US8475937B2 - Silicone composition and organic light-emitting diode - Google Patents
Silicone composition and organic light-emitting diode Download PDFInfo
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- US8475937B2 US8475937B2 US12/933,916 US93391609A US8475937B2 US 8475937 B2 US8475937 B2 US 8475937B2 US 93391609 A US93391609 A US 93391609A US 8475937 B2 US8475937 B2 US 8475937B2
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- United States
- Prior art keywords
- organic
- thiophenyl
- hole
- formula
- silicone composition
- Prior art date
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- 239000000203 mixture Substances 0.000 title claims abstract description 61
- 229920001296 polysiloxane Polymers 0.000 title claims abstract description 43
- -1 polysiloxane Polymers 0.000 claims abstract description 110
- 229910000077 silane Inorganic materials 0.000 claims abstract description 61
- 239000003960 organic solvent Substances 0.000 claims abstract description 50
- 150000004756 silanes Chemical class 0.000 claims abstract description 46
- 230000005525 hole transport Effects 0.000 claims abstract description 39
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 38
- 230000007062 hydrolysis Effects 0.000 claims abstract description 36
- 238000002347 injection Methods 0.000 claims abstract description 35
- 239000007924 injection Substances 0.000 claims abstract description 35
- 239000003431 cross linking reagent Chemical class 0.000 claims abstract description 33
- 239000012074 organic phase Substances 0.000 claims abstract description 24
- 239000008346 aqueous phase Substances 0.000 claims abstract description 21
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 30
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 27
- 150000002894 organic compounds Chemical class 0.000 claims description 26
- 239000000758 substrate Substances 0.000 claims description 23
- 125000001544 thienyl group Chemical group 0.000 claims description 22
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 claims description 20
- 125000001931 aliphatic group Chemical group 0.000 claims description 12
- 239000007850 fluorescent dye Substances 0.000 claims description 6
- 125000000175 2-thienyl group Chemical group S1C([*])=C([H])C([H])=C1[H] 0.000 claims 2
- 239000010410 layer Substances 0.000 description 102
- KRCZLPQTJDWPKN-UHFFFAOYSA-N tribromosilicon Chemical compound Br[Si](Br)Br KRCZLPQTJDWPKN-UHFFFAOYSA-N 0.000 description 32
- PPDADIYYMSXQJK-UHFFFAOYSA-N trichlorosilicon Chemical compound Cl[Si](Cl)Cl PPDADIYYMSXQJK-UHFFFAOYSA-N 0.000 description 32
- 239000000047 product Substances 0.000 description 26
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 24
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 23
- 229920000642 polymer Polymers 0.000 description 23
- 239000003054 catalyst Substances 0.000 description 22
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 22
- 238000000034 method Methods 0.000 description 20
- 229910052751 metal Inorganic materials 0.000 description 19
- 239000002184 metal Substances 0.000 description 19
- 239000010408 film Substances 0.000 description 14
- 125000004432 carbon atom Chemical group C* 0.000 description 13
- 238000006459 hydrosilylation reaction Methods 0.000 description 13
- 229930192474 thiophene Natural products 0.000 description 13
- 150000003577 thiophenes Chemical class 0.000 description 13
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Divinylene sulfide Natural products C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 11
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 10
- 239000011521 glass Substances 0.000 description 10
- 150000001875 compounds Chemical class 0.000 description 9
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 8
- 125000000962 organic group Chemical group 0.000 description 7
- 229910052697 platinum Inorganic materials 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 6
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 6
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 6
- 229920000620 organic polymer Polymers 0.000 description 6
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 description 6
- 239000011541 reaction mixture Substances 0.000 description 6
- 230000035484 reaction time Effects 0.000 description 6
- 238000005160 1H NMR spectroscopy Methods 0.000 description 5
- CAJILKYXPOWWBF-UHFFFAOYSA-N 2-prop-2-enylthiophene Chemical compound C=CCC1=CC=CS1 CAJILKYXPOWWBF-UHFFFAOYSA-N 0.000 description 5
- 239000003377 acid catalyst Substances 0.000 description 5
- 239000011575 calcium Substances 0.000 description 5
- 238000000151 deposition Methods 0.000 description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 5
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 5
- 229920002098 polyfluorene Polymers 0.000 description 5
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 5
- VQUOZKYAOKYDIJ-UHFFFAOYSA-N trichloro(3-thiophen-2-ylpropyl)silane Chemical compound Cl[Si](Cl)(Cl)CCCC1=CC=CS1 VQUOZKYAOKYDIJ-UHFFFAOYSA-N 0.000 description 5
- ZDHXKXAHOVTTAH-UHFFFAOYSA-N trichlorosilane Chemical compound Cl[SiH](Cl)Cl ZDHXKXAHOVTTAH-UHFFFAOYSA-N 0.000 description 5
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 238000013019 agitation Methods 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 4
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 4
- 229910052791 calcium Inorganic materials 0.000 description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 4
- 238000007796 conventional method Methods 0.000 description 4
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 4
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 4
- 239000000413 hydrolysate Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- 239000005052 trichlorosilane Substances 0.000 description 4
- 125000004493 2-methylbut-1-yl group Chemical group CC(C*)CC 0.000 description 3
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 3
- 125000003542 3-methylbutan-2-yl group Chemical group [H]C([H])([H])C([H])(*)C([H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 125000002877 alkyl aryl group Chemical group 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 125000003710 aryl alkyl group Chemical group 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 230000001413 cellular effect Effects 0.000 description 3
- 125000000753 cycloalkyl group Chemical group 0.000 description 3
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 3
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 125000000743 hydrocarbylene group Chemical group 0.000 description 3
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 3
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 125000003538 pentan-3-yl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000007639 printing Methods 0.000 description 3
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 125000003548 sec-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- 125000003944 tolyl group Chemical group 0.000 description 3
- 238000001429 visible spectrum Methods 0.000 description 3
- 239000008096 xylene Substances 0.000 description 3
- 125000005023 xylyl group Chemical group 0.000 description 3
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- JKNRGORPLPITDM-UHFFFAOYSA-N 2-prop-2-enyl-5-thiophen-2-ylthiophene Chemical compound S1C(CC=C)=CC=C1C1=CC=CS1 JKNRGORPLPITDM-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 description 2
- 229920000265 Polyparaphenylene Polymers 0.000 description 2
- 229910003691 SiBr Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 2
- DZBUGLKDJFMEHC-UHFFFAOYSA-N acridine Chemical compound C1=CC=CC2=CC3=CC=CC=C3N=C21 DZBUGLKDJFMEHC-UHFFFAOYSA-N 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 2
- 229910002064 alloy oxide Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- 238000003491 array Methods 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- ZYGHJZDHTFUPRJ-UHFFFAOYSA-N benzo-alpha-pyrone Natural products C1=CC=C2OC(=O)C=CC2=C1 ZYGHJZDHTFUPRJ-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 125000001246 bromo group Chemical group Br* 0.000 description 2
- 230000001680 brushing effect Effects 0.000 description 2
- XJHCXCQVJFPJIK-UHFFFAOYSA-M caesium fluoride Chemical compound [F-].[Cs+] XJHCXCQVJFPJIK-UHFFFAOYSA-M 0.000 description 2
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- WDECIBYCCFPHNR-UHFFFAOYSA-N chrysene Chemical compound C1=CC=CC2=CC=C3C4=CC=CC=C4C=CC3=C21 WDECIBYCCFPHNR-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
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- 235000001671 coumarin Nutrition 0.000 description 2
- 150000004775 coumarins Chemical class 0.000 description 2
- 150000004292 cyclic ethers Chemical class 0.000 description 2
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 239000002019 doping agent Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- BITPLIXHRASDQB-UHFFFAOYSA-N ethenyl-[ethenyl(dimethyl)silyl]oxy-dimethylsilane Chemical compound C=C[Si](C)(C)O[Si](C)(C)C=C BITPLIXHRASDQB-UHFFFAOYSA-N 0.000 description 2
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 2
- 125000001072 heteroaryl group Chemical group 0.000 description 2
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- 229910052739 hydrogen Inorganic materials 0.000 description 2
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- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 2
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- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 125000001624 naphthyl group Chemical group 0.000 description 2
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
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- 125000001424 substituent group Chemical group 0.000 description 2
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 description 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
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- PJANXHGTPQOBST-VAWYXSNFSA-N trans-stilbene Chemical compound C=1C=CC=CC=1/C=C/C1=CC=CC=C1 PJANXHGTPQOBST-VAWYXSNFSA-N 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- KEYINHUVQPCKQK-UHFFFAOYSA-N trichloro-[3-(5-methylthiophen-2-yl)propyl]silane Chemical compound CC1=CC=C(CCC[Si](Cl)(Cl)Cl)S1 KEYINHUVQPCKQK-UHFFFAOYSA-N 0.000 description 2
- KDXBHXLYHQNTSD-UHFFFAOYSA-N trichloro-[3-(5-thiophen-2-ylthiophen-2-yl)propyl]silane Chemical compound S1C(CCC[Si](Cl)(Cl)Cl)=CC=C1C1=CC=CS1 KDXBHXLYHQNTSD-UHFFFAOYSA-N 0.000 description 2
- KPRMUCVZLYMSJX-UHFFFAOYSA-N trichloro-[3-[5-(5-methylthiophen-2-yl)thiophen-2-yl]propyl]silane Chemical compound S1C(C)=CC=C1C1=CC=C(CCC[Si](Cl)(Cl)Cl)S1 KPRMUCVZLYMSJX-UHFFFAOYSA-N 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 238000007738 vacuum evaporation Methods 0.000 description 2
- 238000002061 vacuum sublimation Methods 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
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- 239000011787 zinc oxide Substances 0.000 description 2
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- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 description 1
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- KTUXVRCLHWLODD-UHFFFAOYSA-N 2-ethenyl-4-methylthiophene Chemical compound CC1=CSC(C=C)=C1 KTUXVRCLHWLODD-UHFFFAOYSA-N 0.000 description 1
- ZDSXWSYLVMUDHI-UHFFFAOYSA-N 2-ethenyl-5-methylthiophene Chemical compound CC1=CC=C(C=C)S1 ZDSXWSYLVMUDHI-UHFFFAOYSA-N 0.000 description 1
- QXKBVFKZDKYFOL-UHFFFAOYSA-N 2-ethenyl-5-thiophen-2-ylthiophene Chemical compound S1C(C=C)=CC=C1C1=CC=CS1 QXKBVFKZDKYFOL-UHFFFAOYSA-N 0.000 description 1
- QFNLJQZPCWTEOE-UHFFFAOYSA-N 2-methyl-5-prop-2-enylthiophene Chemical compound CC1=CC=C(CC=C)S1 QFNLJQZPCWTEOE-UHFFFAOYSA-N 0.000 description 1
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- XKWYJGQHYVSADX-UHFFFAOYSA-N 3-ethenyl-2-methylthiophene Chemical compound CC=1SC=CC=1C=C XKWYJGQHYVSADX-UHFFFAOYSA-N 0.000 description 1
- BOJMHHBWYPDQQH-UHFFFAOYSA-N 3-ethenylthiophene Chemical compound C=CC=1C=CSC=1 BOJMHHBWYPDQQH-UHFFFAOYSA-N 0.000 description 1
- VNRHUKMPAKACFT-UHFFFAOYSA-N 3-prop-2-enyl-2-thiophen-2-ylthiophene Chemical compound C1=CSC(C=2SC=CC=2)=C1CC=C VNRHUKMPAKACFT-UHFFFAOYSA-N 0.000 description 1
- NYAXLWYPCFGKJQ-UHFFFAOYSA-N 3-prop-2-enylthiophene Chemical compound C=CCC=1C=CSC=1 NYAXLWYPCFGKJQ-UHFFFAOYSA-N 0.000 description 1
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 description 1
- GJCOSYZMQJWQCA-UHFFFAOYSA-N 9H-xanthene Chemical compound C1=CC=C2CC3=CC=CC=C3OC2=C1 GJCOSYZMQJWQCA-UHFFFAOYSA-N 0.000 description 1
- 229910001148 Al-Li alloy Inorganic materials 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- JBRZTFJDHDCESZ-UHFFFAOYSA-N AsGa Chemical compound [As]#[Ga] JBRZTFJDHDCESZ-UHFFFAOYSA-N 0.000 description 1
- CBDGJXLKYIKWFJ-UHFFFAOYSA-N CC(C)C1=C(C2=CC=CS2)SC(C2=CC=CS2)=C1.CC(C)C1=C(C2=CC=CS2)SC=C1.CC(C)C1=CC=C(C2=CC=C(C3=CC=CS3)S2)S1.CC(C)C1=CC=C(C2=CC=CS2)S1.CC(C)C1=CC=CS1.CC(C)C1=CSC(C2=CC=CS2)=C1.CC(C)C1=CSC=C1 Chemical compound CC(C)C1=C(C2=CC=CS2)SC(C2=CC=CS2)=C1.CC(C)C1=C(C2=CC=CS2)SC=C1.CC(C)C1=CC=C(C2=CC=C(C3=CC=CS3)S2)S1.CC(C)C1=CC=C(C2=CC=CS2)S1.CC(C)C1=CC=CS1.CC(C)C1=CSC(C2=CC=CS2)=C1.CC(C)C1=CSC=C1 CBDGJXLKYIKWFJ-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 1
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
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- 238000005481 NMR spectroscopy Methods 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
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- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 229910003676 SiBr4 Inorganic materials 0.000 description 1
- 229910003910 SiCl4 Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
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- 230000002378 acidificating effect Effects 0.000 description 1
- 125000002015 acyclic group Chemical group 0.000 description 1
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- 229910052783 alkali metal Inorganic materials 0.000 description 1
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- 125000003342 alkenyl group Chemical group 0.000 description 1
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- 229920005603 alternating copolymer Polymers 0.000 description 1
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- 125000003277 amino group Chemical group 0.000 description 1
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- 125000000732 arylene group Chemical group 0.000 description 1
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
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- 229910052799 carbon Inorganic materials 0.000 description 1
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- 239000000919 ceramic Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 125000000068 chlorophenyl group Chemical group 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 125000000490 cinnamyl group Chemical group C(C=CC1=CC=CC=C1)* 0.000 description 1
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- 125000005266 diarylamine group Chemical group 0.000 description 1
- 125000004188 dichlorophenyl group Chemical group 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
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- 238000005516 engineering process Methods 0.000 description 1
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- 239000003822 epoxy resin Substances 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- GVEPBJHOBDJJJI-UHFFFAOYSA-N fluoranthrene Natural products C1=CC(C2=CC=CC=C22)=C3C2=CC=CC3=C1 GVEPBJHOBDJJJI-UHFFFAOYSA-N 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
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- 239000011888 foil Substances 0.000 description 1
- 239000005350 fused silica glass Substances 0.000 description 1
- 125000003976 glyceryl group Chemical group [H]C([*])([H])C(O[H])([H])C(O[H])([H])[H] 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
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- 150000007857 hydrazones Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 229910003437 indium oxide Inorganic materials 0.000 description 1
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- QDLAGTHXVHQKRE-UHFFFAOYSA-N lichenxanthone Natural products COC1=CC(O)=C2C(=O)C3=C(C)C=C(OC)C=C3OC2=C1 QDLAGTHXVHQKRE-UHFFFAOYSA-N 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- JLUFWMXJHAVVNN-UHFFFAOYSA-N methyltrichlorosilane Chemical compound C[Si](Cl)(Cl)Cl JLUFWMXJHAVVNN-UHFFFAOYSA-N 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 150000001282 organosilanes Chemical class 0.000 description 1
- 125000005375 organosiloxane group Chemical group 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- 150000004866 oxadiazoles Chemical class 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920000553 poly(phenylenevinylene) Polymers 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002620 polyvinyl fluoride Polymers 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 1
- 125000002568 propynyl group Chemical group [*]C#CC([H])([H])[H] 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- WVIICGIFSIBFOG-UHFFFAOYSA-N pyrylium Chemical compound C1=CC=[O+]C=C1 WVIICGIFSIBFOG-UHFFFAOYSA-N 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000001552 radio frequency sputter deposition Methods 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical class [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 1
- KCIKCCHXZMLVDE-UHFFFAOYSA-N silanediol Chemical group O[SiH2]O KCIKCCHXZMLVDE-UHFFFAOYSA-N 0.000 description 1
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 1
- AIFMYMZGQVTROK-UHFFFAOYSA-N silicon tetrabromide Chemical compound Br[Si](Br)(Br)Br AIFMYMZGQVTROK-UHFFFAOYSA-N 0.000 description 1
- FDNAPBUWERUEDA-UHFFFAOYSA-N silicon tetrachloride Chemical compound Cl[Si](Cl)(Cl)Cl FDNAPBUWERUEDA-UHFFFAOYSA-N 0.000 description 1
- 239000005049 silicon tetrachloride Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 150000001629 stilbenes Chemical class 0.000 description 1
- 235000021286 stilbenes Nutrition 0.000 description 1
- 125000005504 styryl group Chemical group 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- DFQPZDGUFQJANM-UHFFFAOYSA-M tetrabutylphosphanium;hydroxide Chemical compound [OH-].CCCC[P+](CCCC)(CCCC)CCCC DFQPZDGUFQJANM-UHFFFAOYSA-M 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- JFLKFZNIIQFQBS-FNCQTZNRSA-N trans,trans-1,4-Diphenyl-1,3-butadiene Chemical compound C=1C=CC=CC=1\C=C\C=C\C1=CC=CC=C1 JFLKFZNIIQFQBS-FNCQTZNRSA-N 0.000 description 1
- PJANXHGTPQOBST-UHFFFAOYSA-N trans-Stilbene Natural products C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 description 1
- TVIVIEFSHFOWTE-UHFFFAOYSA-K tri(quinolin-8-yloxy)alumane Chemical compound [Al+3].C1=CN=C2C([O-])=CC=CC2=C1.C1=CN=C2C([O-])=CC=CC2=C1.C1=CN=C2C([O-])=CC=CC2=C1 TVIVIEFSHFOWTE-UHFFFAOYSA-K 0.000 description 1
- 125000005259 triarylamine group Chemical group 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- GFJGILDCJZMQTN-UHFFFAOYSA-N trichloro(8-trichlorosilyloctyl)silane Chemical compound Cl[Si](Cl)(Cl)CCCCCCCC[Si](Cl)(Cl)Cl GFJGILDCJZMQTN-UHFFFAOYSA-N 0.000 description 1
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- YVTHLONGBIQYBO-UHFFFAOYSA-N zinc indium(3+) oxygen(2-) Chemical compound [O--].[Zn++].[In+3] YVTHLONGBIQYBO-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
- C08L83/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
- C08G77/28—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen sulfur-containing groups
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/40—Organosilicon compounds, e.g. TIPS pentacene
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/14—Carrier transporting layers
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/17—Carrier injection layers
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/17—Carrier injection layers
- H10K50/171—Electron injection layers
Definitions
- the present invention relates to a silicone composition and more particularly to a silicone composition
- a silicone composition comprising (A) a hydrolysis product prepared by reacting at least one thiophenyl-substituted silane and a cross-linking agent with water in the presence of an organic solvent to form an organic phase containing the hydrolysis product and an aqueous phase, and separating the organic phase from the aqueous phase; and (B) an organic solvent.
- the present invention also relates to an organic light-emitting diode (OLED) containing a hole-transport/hole-injection layer comprising a cured polysiloxane prepared by applying the aforementioned silicone composition to form a film and curing the film.
- OLED organic light-emitting diode
- OLEDs Organic light-emitting diodes
- LCDs liquid-crystal displays
- OLED displays are thinner, consume less power, and are brighter than LCDs.
- OLED displays are self-luminous and do not require backlighting.
- OLED displays have a wide viewing angle, even in bright light. As a result of these combined features, OLED displays are lighter in weight and take up less space than LCD displays.
- OLEDs typically comprise a light-emitting element interposed between an anode and a cathode.
- the light-emitting element typically comprises a stack of thin organic layers comprising a hole-transport layer, an emissive layer, and an electron-transport layer.
- OLEDs can also contain additional layers, such as a hole-injection layer and an electron-injection layer.
- the emissive layer can contain a fluorescent dye or dopant to enhance the electroluminescent efficiency of the OLED and control color output.
- PDOT:PSS poly(3,4-ethylenedioxythiophene)poly(styrenesulfonate), PDOT:PSS
- PDOT:PSS poly(3,4-ethylenedioxythiophene)poly(styrenesulfonate)
- OLEDs containing this material typically have a low turn-on voltage and high brightness.
- a hole-transport layer comprising PDOT:PSS has many limitations including low transparency, high acidity, susceptibility to electrochemical de-doping (migration of dopant from hole-transport layer) and electrochemical decomposition.
- PDOT:PSS is insoluble in organic solvents and aqueous emulsions of the polymer, used to prepare the hole-transport layer, have limited stability. Consequently, there is a need for an OLED comprising a hole-transport layer that overcomes the aforementioned limitations.
- the present invention is directed to a silicone composition
- a silicone composition comprising:
- A a hydrolysis product prepared by reacting (a) at least one thiophenyl-substituted silane having the formula Th—(CH 2 ) m+2 SiR 1 n X 3-n , and (b) a cross-linking agent selected from (i) at least one silane having the formula (R 3 b SiX 4-b ), (ii) at least one organic compound having an average of at least two silyl groups per molecule, wherein the silyl groups have the formula —SiR 3 c X 3-c , and (iii) a mixture comprising (i) and (ii), with water in the presence of an organic solvent to form an organic phase containing the hydrolysis product and an aqueous phase, and separating the organic phase from the aqueous phase, wherein R 1 is C 1 to C 10 hydrocarbyl free of aliphatic unsaturation, X is a hydrolysable group, Th is thiophenyl or substituted thiophenyl, R
- the present invention is also directed to an organic light-emitting diode comprising:
- a substrate having a first opposing surface and a second opposing surface
- the light-emitting element comprising
- the OLED of the present invention has a low turn-on voltage and high brightness.
- the hole-transport/hole-injection layer of the present invention which comprises a cured polysiloxane, exhibits high transparency and a neutral pH.
- the hydrolysis product in the silicone composition used to prepare the hole-transport/hole-injection layer is soluble in organic solvents, and the composition has good stability in the absence of moisture.
- the organic light-emitting diode of the present invention is useful as a discrete light-emitting device or as the active element of light-emitting arrays or displays, such as flat panel displays.
- OLED displays are useful in a number of devices, including watches, telephones, lap-top computers, pagers, cellular phones, digital video cameras, DVD players, and calculators.
- FIG. 1 shows a cross-sectional view of a first embodiment of an OLED according to the present invention.
- FIG. 2 shows a cross-sectional view of a second embodiment of an OLED according to the present invention.
- the term “overlying” used in reference to the position of the first electrode layer, light-emitting element, and second electrode layer relative to the designated component means the particular layer either lies directly on the component or lies above the component with one or more intermediate layers there between, provided the OLED is oriented with the substrate below the first electrode layer as shown in FIGS. 1 and 2 .
- the term “overlying” used in reference to the position of the first electrode layer relative to the first opposing surface of the substrate in the OLED means the first electrode layer either lies directly on the surface or is separated from the surface by one or more intermediate layers.
- a silicone composition according to the present invention comprises:
- A a hydrolysis product prepared by reacting (a) at least one thiophenyl-substituted silane having the formula Th—(CH 2 ) m+2 SiR 1 n X 3-n , and (b) a cross-linking agent selected from (i) at least one silane having the formula (R 3 b SiX 4-b ), (ii) at least one organic compound having an average of at least two silyl groups per molecule, wherein the silyl groups have the formula —SiR 3 c X 3-c , and (iii) a mixture comprising (i) and (ii), with water in the presence of an organic solvent to form an organic phase containing the hydrolysis product and an aqueous phase, and separating the organic phase from the aqueous phase, wherein R 1 is C 1 to C 10 hydrocarbyl free of aliphatic unsaturation, X is a hydrolysable group, Th is thiophenyl or substituted thiophenyl, R
- Component (A) of the silicone composition is a hydrolysis product prepared by reacting (a) at least one thiophenyl-substituted silane having the formula Th—(CH 2 ) m+2 SiR 1 n X 3-n , and (b) a cross-linking agent selected from (i) at least one silane having the formula (R 3 b SiX 4-b ), (ii) at least one organic compound having an average of at least two silyl groups per molecule, wherein the silyl groups have the formula —SiR 3 c X 3-c , and (iii) a mixture comprising (i) and (ii), with water in the presence of an organic solvent to form an organic phase containing the hydrolysis product and an aqueous phase, and separating the organic phase from the aqueous phase, wherein R 1 is C 1 to C 10 hydrocarbyl free of aliphatic unsaturation, X is a hydrolysable group, Th is thiophenyl or substituted
- the thiophenyl-substituted silane (a) is at least one thiophenyl-substituted silane having the formula Th—(CH 2 ) m+2 SiR 1 n X 3-n , wherein R 1 is C 1 to C 10 hydrocarbyl free of aliphatic unsaturation, X is a hydrolysable group, Th is thiophenyl or substituted thiophenyl, m is 0 to 10, and n is 0, 1, or 2.
- the subscript m has a value of from 0 to 5 or from 1 to 3.
- the hydrocarbyl groups represented by R 1 are free of aliphatic unsaturation and typically have from 1 to 10 carbon atoms, alternatively from 1 to 6 carbon atoms.
- the term “free of aliphatic unsaturation” means the group is free of aliphatic carbon-carbon double bonds and aliphatic carbon-carbon triple bonds.
- Acyclic hydrocarbyl groups containing at least 3 carbon atoms can have a branched or unbranched structure.
- hydrocarbyl groups represented by R 1 include, but are not limited to, alkyl, such as methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, 1,1-dimethylethyl, pentyl, 1-methylbutyl, 1-ethylpropyl, 2-methylbutyl, 3-methylbutyl, 1,2-dimethylpropyl, 2,2-dimethylpropyl, hexyl, heptyl, octyl, nonyl, and decyl; cycloalkyl, such as cyclopentyl, cyclohexyl, and methylcyclohexyl; aryl, such as phenyl and naphthyl; alkaryl, such as tolyl and xylyl; and aralkyl, such as benzyl and phenethyl.
- alkyl such as methyl, ethyl, prop
- X denotes a hydrolysable group.
- hydrolysable group means the silicon-bonded group reacts with water in either the presence or absence of a catalyst at any temperature from room temperature ( ⁇ 23 ⁇ 2° C.) to 100° C. within several minutes, for example thirty minutes, to form a silanol (Si—OH) group.
- hydrolysable groups represented by X include, but are not limited to, —Cl, —Br, —OR 2 , —OCH 2 CH 2 OR 2 , CH 3 C( ⁇ O)O—, Et(Me)C ⁇ N—O—, CH 3 C( ⁇ O)N(CH 3 )—, and —ONH 2 , wherein R 2 is C 1 to C 8 hydrocarbyl or C 1 to C 8 halogen-substituted hydrocarbyl, both free of aliphatic unsaturation.
- the hydrocarbyl and halogen-substituted hydrocarbyl groups represented by R 2 are free of aliphatic unsaturation and typically have from 1 to 8 carbon atoms, alternatively from 3 to 6 carbon atoms.
- Acyclic hydrocarbyl and halogen-substituted hydrocarbyl groups containing at least 3 carbon atoms can have a branched or unbranched structure.
- hydrocarbyl groups include, but are not limited to, unbranched and branched alkyl, such as methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, 1,1-dimethylethyl, pentyl, 1-methylbutyl, 1-ethylpropyl, 2-methylbutyl, 3-methylbutyl, 1,2-dimethylpropyl, 2,2-dimethylpropyl, hexyl, heptyl, and octyl; cycloalkyl, such as cyclopentyl, cyclohexyl, and methylcyclohexyl; phenyl; alkaryl, such as tolyl and xylyl; and aralkyl, such as benzyl and phenethyl.
- halogen-substituted hydrocarbyl groups include, but are not limited to, 3,3,3-trifluoropropyl
- Th denotes a thiophenyl group or substituted thiophenyl group.
- thiophenyl refers to a monovalent organic group containing a least one 5-membered heteroaromatic ring having the heteroatom sulfur and a free valence at a ring carbon atom.
- Examples of thiophenyl groups represented by Th include, but are not limited to, groups having the following formulae:
- substituted thiophenyl means the thiophenyl group, described above, has a substituent replacing hydrogen on one or more positions of one or more heteroaromatic rings.
- substituents include, but are not limited to, alkyl such as methyl, ethyl, propyl, butyl, pentyl, and hexyl; aryl such as phenyl; and halo such as chloro and bromo.
- the thiophenyl-substituted silane (a) can be a single silane or a mixture comprising two or more different thiophenyl-substituted silanes, each as described and exemplified above.
- the thiophenyl-substituted silane can be prepared by reacting (i) an alkenyl-substituted thiophene having the formula Th—(CH 2 ) m CH ⁇ CH 2 with (ii) a silane having the formula HR 1 n SiX 3-n in the presence of (iii) a hydrosilylation catalyst and, optionally, (iv) an organic solvent, wherein R 1 , Th, X, m, and n are as defined and exemplified above for the thiophenyl-substituted silane.
- the alkenyl-substituted thiophene (i) has the formula Th—(CH 2 ) m CH ⁇ CH 2 wherein Th and m are as defined and exemplified above for the thiophenyl-substituted silane.
- alkenyl-substituted thiophenes include, but are not limited to, 2-vinylthiophene, 3-vinylthiophene, 2-allylthiophene, 3-allylthiophene, 4-methyl-2-vinylthiophene, 3-methyl-2-vinylthiophene, 2-methyl-3-vinylthiophene, 5-methyl-2-vinylthiophene, 5-vinyl-2,2′-bithiophene, 3-(2-propenyl)-2,2′-bithiophene, 5-(2-propenyl)-2,2′-bithiophene, 5-vinyl-2,2′:5′,2′′-terthiophene, 3′-vinyl-2,2′:5′,2′′-terthiophene, and 5-ethyl-5′′-vinyl-2,2′:5′,2′′-terthiophene.
- methods of preparing alkenyl-substituted include, but
- the silane (ii) has the formula HR 1 n SiX 3-n wherein R 1 , X, and n are as defined and exemplified above for the thiophenyl-substituted silane.
- silanes suitable for use as silane (ii) include, but are not limited to, halosilanes such as HSiCl 3 , HSiBr 3 , HMeSiCl 2 , HEtSiCl 2 , HMeSiBr 2 , HEtSiBr 2 , HPhSiCl 2 , HPhSiBr 2 , BuHSiCl 2 , and i-PrHSiCl 2 , HMe 2 SiCl, HMe 2 SiBr, HEt 2 SiCl, and HEt 2 SiBr; alkoxysilanes such as HSi(OMe) 3 , HSi(OEt) 3 , HSi(OPr) 3 ,
- the hydrosilylation catalyst (iii) can be any of the well-known hydrosilylation catalysts comprising a platinum group metal (i.e., platinum, rhodium, ruthenium, palladium, osmium and iridium) or a compound containing a platinum group metal.
- a platinum group metal i.e., platinum, rhodium, ruthenium, palladium, osmium and iridium
- the platinum group metal is platinum, based on its high activity in hydrosilylation reactions.
- Preferred hydrosilylation catalysts include the complexes of chloroplatinic acid and certain vinyl-containing organosiloxanes disclosed by Willing in U.S. Pat. No. 3,419,593, which is hereby incorporated by reference.
- a preferred catalyst of this type is the reaction product of chloroplatinic acid and 1,3-diethenyl-1,1,3,3-tetramethyldisiloxane.
- the organic solvent (iv) is at least one organic solvent.
- the organic solvent can be any aprotic or dipolar aprotic organic solvent that does not react with the alkenyl-substituted thiophene (i), the silane (ii), or the thiophenyl-substituted silane product under the conditions of the present method, and is miscible with components (i), (ii), and the thiophenyl-substituted silane.
- organic solvents include, but are not limited to, saturated aliphatic hydrocarbons such as n-pentane, hexane, n-heptane, isooctane and dodecane; cycloaliphatic hydrocarbons such as cyclopentane and cyclohexane; aromatic hydrocarbons such as benzene, toluene, xylene and mesitylene; cyclic ethers such as tetrahydrofuran (THF) and dioxane; ketones such as methyl isobutyl ketone (MIBK); halogenated alkanes such as trichloroethane; and halogenated aromatic hydrocarbons such as bromobenzene and chlorobenzene.
- Organic solvent (iv) can be a single organic solvent or a mixture comprising two or more different organic solvents, each as defined above.
- the reaction of the alkenyl-substituted thiophene (i) with the silane (ii) can be carried out in any standard reactor suitable for hydrosilylation reactions. Suitable reactors include glass and Teflon-lined glass reactors. Preferably, the reactor is equipped with a means of agitation, such as stirring. Also, preferably, the reaction is carried out in an inert atmosphere, such as nitrogen or argon, in the absence of moisture.
- the alkenyl-substituted thiophene (i), silane (ii), hydrosilylation catalyst (iii), and, optionally, organic solvent (iv) can be combined in any order.
- the silane (ii) is added to a mixture of the alkenyl-substituted thiophene, hydrosilylation catalyst, and, optionally, organic solvent.
- the reaction is typically carried out at a temperature of from 50 to 120° C., alternatively from room temperature ( ⁇ 23 ⁇ 2° C.) to 70° C. When the temperature is less than room temperature, the rate of reaction is typically very slow.
- the reaction time depends on several factors, such as the structures of the alkenyl-substituted thiophene (i) and the silane (ii), and the temperature.
- the time of reaction is typically from 2 to 4 h at a temperature of from 50 to 70° C.
- the optimum reaction time can be determined by routine experimentation using the methods set forth in the Examples section below.
- the ratio of the number of moles of the silane (ii) to the number of moles of the alkenyl-substituted thiophene (i) is typically from 1 to 5, alternatively from 1 to 3, alternatively from 1 to 2.
- the alkneyl-substituted thiophene may be used in excess relative to the silane.
- the concentration of hydrosilylation catalyst (iii) is sufficient to catalyze the addition reaction of the alkenyl-substituted thiophene (i) with the silane (ii).
- the concentration of hydrosilylation catalyst is sufficient to provide from 0.1 to 1000 ppm of a platinum group metal, alternatively from 1 to 500 ppm of a platinum group metal, alternatively from 5 to 150 ppm of a platinum group metal, based on the combined weight of the alkenyl-substituted thiophene (i) and the silane (ii).
- the rate of reaction is very slow below 0.1 ppm of platinum group metal.
- the use of more than 1000 ppm of platinum group metal results in no appreciable increase in reaction rate, and is therefore uneconomical.
- the concentration of organic solvent (iv) is typically from 10 to 70% (w/w), alternatively from 20 to 50% (w/w), alternatively from 30 to 40% (w/w), based on the total weight of the reaction mixture.
- the thiophenyl-substituted silane can be recovered from the reaction mixture using conventional separation/purification methods, such as distillation and chromatography.
- the cross-linking agent (b) is selected from (i) at least one silane having the formula (R 3 b SiX 4-b ), (ii) at least one organic compound having an average of at least two silyl groups per molecule, wherein the silyl groups have the formula —SiR 3 c X 3-c , and (iii) a mixture comprising (i) and (ii), wherein X is a hydrolysable group, R 3 is C 1 to C 10 hydrocarbyl or —H, b is 0 or 1, and c is 0, 1, or 2.
- Cross-linking agent (b)(i) is at least one silane having the formula (R 3 b SiX 4-b ), where X, and b are as defined and exemplified above and R 3 is C 1 to C 10 hydrocarbyl or —H.
- the hydrocarbyl groups represented by R 3 typically have from 1 to 10 carbon atoms, alternatively from 1 to 6 carbon atoms, alternatively from 1 to 4 carbon atoms.
- Acyclic hydrocarbyl and halogen-substituted hydrocarbyl groups containing at least 3 carbon atoms can have a branched or unbranched structure.
- hydrocarbyl groups include, but are not limited to, alkyl, such as methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, 1,1-dimethylethyl, pentyl, 1-methylbutyl, 1-ethylpropyl, 2-methylbutyl, 3-methylbutyl, 1,2-dimethylpropyl, 2,2-dimethylpropyl, hexyl, heptyl, octyl, nonyl, and decyl; cycloalkyl, such as cyclopentyl, cyclohexyl, and methylcyclohexyl; aryl, such as phenyl and naphthyl; alkaryl, such as tolyl and xylyl; aralkyl, such as benzyl and phenethyl; alkenyl, such as vinyl, allyl, and propenyl; ary
- silanes suitable for use as cross-linking agent (b)(i) include, but are not limited to, silanes having the following formulae: SiCl 4 , SiBr 4 , Si(OMe) 4 , Si(OEt) 4 , MeSiCl 3 , MeSiBr 3 , MeSi(OMe) 3 , EtSiCl 3 , EtSiBr 3 , EtSi(OMe) 3 , MeSi(OEt) 3 , EtSi(OEt) 3 , PhSiCl 3 , PhSiBr 3 , PhSi(OMe) 3 , and PhSi(OEt) 3 .
- the cross-linking agent (b)(i) can be a single silane or a mixture comprising two or more different silanes, each having the formula (R 3 b SiX 4-b ), wherein R 3 , X, and b are as defined and exemplified above.
- methods of preparing silanes having hydrolysable groups are well known in the art; many of these compounds are commercially available.
- the cross-linking agent (b)(ii) is at least one organic compound having an average of at least two silyl groups per molecule, wherein the silyl groups have the formula —SiR 3 c X 3-c , wherein R 3 , X, and c are as defined and exemplified above.
- the organic compound can be a discrete compound or a polymer.
- organic compounds suitable for use as cross-linking agent (b)(ii) include, but are not limited to organic compounds having the formulae R 4 (SiR 3 c X 3-c ) 2 , R 5 (SiR 3 c X 3-c ) 3 , and R 6 (SiR 3 c X 3-c ) 4 , wherein R 3 , X, and c are as defined and exemplified above, R 4 is a divalent organic group, R 5 is a trivalent organic group, and R 6 is a tetravalent organic group. Examples of divalent organic groups include, but are not limited to, hydrocarbylene and carbazolediyl.
- the hydrocarbylene groups represented by R 4 typically have from 1 to 10 carbon atoms, alternatively from 1 to 6 carbon atoms, alternatively 1 to 4 carbon atoms.
- hydrocarbylene groups include, but are not limited to, alkylene such as methylene, ethylene, propane-1,3-diyl, 2-methylpropane-1,3-diyl, butane-1,4-diyl, butane-1,3-diyl, pentane-1,5-diyl, pentane-1,4-diyl, hexane-1,6-diyl, octane-1,8-diyl, and decane-1,10-diyl; cycloalkylene such as cyclohexane-14-diyl; and arylene such as 1,2-phenylene, 1,3-phenylene, and 1,4-phenylene.
- carbazolediyl groups include, but are not limited to, carbazole-1,9-diyl, carbazole-2,9-diyl, carbazole-3,9-diyl, carbazole-4,9-diyl, carbazole-2,7-diyl, carbazole-3,6-diyl, 9-methylcarbazole-2,7-diyl, 9-methylcarbazole-3,6-diyl, 9-ethylcarbazole-2,7-diyl, 9-ethylcarbazole-3,6-diyl, 9-propylcarbazole-2,7-diyl, 9-propylcarbazole-3,6-diyl, 9-butylcarbazole-2,7-diyl, 9-butylcarbazole-3,6-diyl, 9-phenylcarbazole-2,7-diyl, and 9-phenyl
- Examples of organic compounds having the formula R 4 (SiR 3 c X 3-c ) 2 wherein R 3 , R 4 , X, and c are as defined and exemplified above, include, but are not limited to, compounds having the following formulae: Cl 3 Si(CH 2 ) 2 SiCl 3 , Cl 3 Si(CH 2 ) 3 SiCl 3 , Cl 3 Si(CH 2 ) 4 SiCl 3 , Cl 3 Si(CH 2 ) 5 SiCl 3 , Cl 3 Si(CH 2 ) 6 SiCl 3 , Cl 3 Si(CH 2 ) 8 SiCl 3 , Cl 3 Si(CH 2 ) 10 SiCl 3 , Cl 3 SiC 6 H 4 SiCl 3 , Br 3 Si(CH 2 ) 2 SiBr 3 , Br 3 Si(CH 2 ) 3 SiBr 3 , Br 3 Si(CH 2 ) 4 SiBr 3 , Br 3 Si(CH 2 ) 5 SiBr 3 , Br 3 Si(CH 2 ) 6 SiB
- Examples of trivalent organic groups represented by R 5 include, but are not limited to, propane-1,2,3-triyl, butane-1,2,3-triyl, butane-1,2,4-triyl, pentane-1,2,3-triyl, pentane-1,3,4-triyl, pentane-1,3,5-triyl, hexane-1,2,3-triyl, hexane-1,2,4-triyl, hexane-1,2,6-triyl, hexane-1,3,4-triyl, hexane-1,3,6-triyl, octane-1,2,3-triyl, octane-1,3,6-triyl, octane-1,3,8-triyl, octane-1,4,6-triyl, octane-1,4,8-triyl, cyclohexane-1,2,3-triyl, cycl
- Examples of organic compounds having the formula R 5 (SiR 3 c X 3-c ) 3 wherein R 3 , R 5 , X, and c are as defined and exemplified above, include, but are not limited to, compounds having the following formulae: Cl 3 SiCH 2 CH(SiCl 3 )CH 2 SiCl 3 , Cl 3 SiCH 2 CH(SiCl 3 )CH(SiCl 3 )CH 3 , Cl 3 SiCH 2 CH(SiCl 3 )CH 2 CH 2 (SiCl 3 ), Cl 3 SiCH 2 CH 2 CH(SiCl 3 )CH 2 CH 2 SiCl 3 , Cl 3 SiCH 2 CH(SiCl 3 )CH 2 CH 2 CH 2 SiCl 3 , Cl 3 SiCH 2 CH(SiCl 3 )CH(SiCl 3 )CH 2 CH 2 CH 3 , Br 3 SiCH 2 CH(SiBr 3 )CH 2 SiBr 3 , Br 3 SiCH 2 CH(Si
- Examples of tetravalent organic groups represented by R 6 include, but are not limited to, butane-1,2,3,4-tetrayl, pentane-1,2,3,4-tetrayl, pentane-1,2,3,5-tetrayl, pentane-1,2,4,5-tetrayl, hexane-1,2,3,4-tetrayl, hexane-1,2,3,5-tetrayl, hexane-1,2,3,6-tetrayl, hexane-1,3,4,5-tetrayl, hexane-1,3,4,6-tetrayl, octane-1,2,3,4-tetrayl, octane-1,2,3,6-tetrayl, octane-1,2,3,8-tetrayl, octane-1,3,4,8-tetrayl, octane-1,3,4,8-tet
- Examples of organic compounds having the formula R 6 (SiR 3 c X 3-c ) 4 wherein R 3 , R 6 , X, and c are as defined and exemplified above, include, but are not limited to, compounds having the following formulae: Cl 3 SiCH 2 CH(SiCl 3 )CH(SiCl 3 )CH 2 (SiCl 3 ), Cl 3 SiCH 2 CH 2 (SiCl 3 )CH(SiCl 3 )CH(SiCl 3 )CH 3 , Cl 3 SiCH 2 CH 2 (SiCl 3 )CH(SiCl 3 )CH 2 CH 2 SiCl 3 ; Cl 3 SiCH 2 CH 2 (SiCl 3 )CH 2 CH(SiCl 3 )CH 2 SiCl 3 , Cl 3 SiCH 2 CH(SiCl 3 )CH(SiCl 3 )CH(SiCl 3 )CH 2 CH 3 , Cl 3 SiCH 2 CH(SiCl 3
- the organic compound can also be a polymer having an average of at least two silyl groups per molecule.
- the polymer can be a homopolymer containing identical repeat units or a copolymer containing two or more different repeat units. In a copolymer, the units can be in any order.
- the polymer can be a random, alternating, or block copolymer.
- the polymer typically has a number-average molecular weight of from 500 to 100,000, alternatively from 1000 to 10,000, alternatively from 2000 to 5000.
- polymers include, but are not limited to, polymers having the following formulae: —[CH(OCH 2 CH 2 SiCl 3 )CH 2 ]—, —[CH(OCH 2 CH 2 CH 2 SiCl 3 )CH 2 ]—, —[CH(C 6 H 4 OCH 2 CH 2 SiCl 3 )CH 2 ]—, —[CH(C 6 H 4 OCH 2 CH 2 CH 2 SiCl 3 )CH 2 ]—, —[Si(CH 3 )(CH 2 CH 2 SiCl 3 )O]—, —[CH(OCH 2 CH 2 SiBr 3 )CH 2 ]—; —[CH(OCH 2 CH 2 CH 2 SiBr 3 )CH 2 ]—; —[CH(C 6 H 4 OCH 2 CH 2 SiBr 3 )CH 2 ]—, —[CH(C 6 H 4 OCH 2 CH 2 CH 2 SiBr 3 )CH 2 ]—, —[Si(CH 3 )CH
- the cross-linking agent (b)(ii) can be a single organic compound or a mixture comprising two or more different organic compounds, each as described and exemplified above. Moreover, methods of preparing organic compounds having silyl groups are well known in the art.
- the cross-linking agent (b)(iii) is a mixture comprising (b)(i) and (b)(ii), each as described and exemplified above.
- the thiophenyl-substituted silane and cross-linking agent are reacted with water in the presence of an organic solvent.
- the organic solvent can be any aprotic or dipolar aprotic organic solvent that is partially miscible or immiscible with water, does not react with the thiophenyl-substituted silane (a), the cross-linking agent (b), or the hydrolysis product under the conditions of the present method, and is miscible with the thiophenyl-substituted silane (a), the cross-linking agent (b), and the hydrolysis product.
- the term “partially miscible” means that the solubility of water in the solvent is less than about 0.1 g/100 g of solvent at 25° C.
- organic solvents include, but are not limited to, saturated aliphatic hydrocarbons such as n-pentane, hexane, n-heptane, isooctane and dodecane; cycloaliphatic hydrocarbons such as cyclopentane and cyclohexane; aromatic hydrocarbons such as benzene, toluene, xylene and mesitylene; cyclic ethers such as tetrahydrofuran (THF) and dioxane; ketones such as methyl isobutyl ketone (MIBK); halogenated alkanes such as trichloroethane; and halogenated aromatic hydrocarbons such as bromobenzene and chlorobenzene.
- the organic solvent can be a single organic solvent or a mixture comprising two or more different organic solvents, each as described above.
- the reaction of the thiophenyl-substituted silane (a) and the cross-linking agent (b) with water can be carried out in any standard reactor suitable for contacting organohalosilanes with water.
- Suitable reactors include glass and Teflon-lined glass reactors.
- the reactor is equipped with a means of agitation, such as stirring.
- the thiophenyl-substituted silane (a), the cross-linking agent (b), and water are typically combined by adding the water to a mixture of components (a), (b), and the organic solvent.
- Reverse addition i.e., addition of the thiophenyl-substituted silane (a) and the cross-linking agent (b) to water is also possible.
- reverse addition may result in formation of a gel.
- the rate of addition of water to the thiophenyl-substituted silane (a) and the cross-linking agent (b) is typically from 0.1 to 1 mL/min. for a 1000-mL reaction vessel equipped with an efficient means of stirring. When the rate of addition is too slow, the reaction time is unnecessarily prolonged. When the rate of addition is too fast, the reaction mixture may form a gel.
- the reaction of the thiophenyl-substituted silane (a) and the cross-linking agent (b) with water is typically carried out at a temperature of from ⁇ 78 to 25° C., alternatively from ⁇ 78 to 0° C., alternatively from ⁇ 78 to ⁇ 50° C.
- the reaction time depends on several factors, including the structures of the thiophenyl-substituted silane (a) and the cross-linking agent (b), and the temperature.
- the reaction is typically carried out for an amount of time sufficient to complete hydrolysis of the thiophenyl-substituted silane (a) and the cross-linking agent (b).
- the term “to complete hydrolysis” means that at least 85 mol % of the silicon-bonded groups —X originally present in the thiophenyl-substituted silane (a) and the cross-linking agent (b) are converted to silicon-bonded hydroxy groups.
- the reaction time is typically from 10 to 240 min., alternatively from 30 to 180 min., alternatively from 60 to 120 min., at a temperature of from ⁇ 78 to ⁇ 50° C.
- the optimum reaction time can be determined by routine experimentation using the methods set forth in the Examples section below.
- the concentration of the thiophenyl-substituted silane (a) is typically from 50 to 95 mol %, alternatively from 60 to 90 mol %, alternatively from 70 to 80 mol %, based on the sum of the number of moles of components (a) and (b).
- the concentration of the organic solvent is typically from 50 to 90% (w/w), alternatively from 60 to 80% (w/w), alternatively from 70 to 75% (w/w), based on the total weight of the reaction mixture.
- the concentration of water in the reaction mixture is typically sufficient to effect hydrolysis of the thiophenyl-substituted silane (a) and the cross-linking agent (b).
- the concentration of water is typically such that the ratio of the number of moles of water to the sum of the number of moles of the silicon-bonded groups —X in the thiophenyl-substituted silane (a) and the cross-linking agent (b) is from 1 to 10, alternatively from 2 to 5.
- the reaction mixture can further comprise at least one hydrolysis catalyst.
- the hydrolysis catalyst can be any acid catalyst or basic catalyst typically used to catalyze the hydrolysis of organosilanes containing hydrolysable groups that do not react with water to form an acid or a base.
- acid catalysts include, but are not limited to, inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, and hydrofluoric acid; and organic acids such as acetic acid, oxalic acid, and trifluoroacetic acid.
- the acid catalyst can be a single acid catalyst or a mixture comprising two or more different acid catalysts.
- alkali catalysts include, but are not limited to, inorganic bases such as ammonium hydroxide; and organic bases such as tetramethylammonium hydroxide, tetrabutylammonium hydroxide, and tetrabutylphosphonium hydroxide.
- the alkali catalyst can be a single alkali catalyst or a mixture comprising two or more different alkali catalysts.
- the organic phase containing the hydrolysis product is separated from the aqueous phase.
- This separation can be achieved using conventional methods.
- the organic phase can be separated from the aqueous phase by discontinuing agitation of the mixture, allowing the mixture to separate into two layers, an organic phase and an aqueous phase, and removing the organic phase containing the hydrolysis product.
- the organic phase is typically washed with water until the wash has a neutral pH. Residual water can be removed from the organic phase using conventional methods such as evaporation under reduced pressure.
- the organic solvent typically either forms a minimum boiling azeotrope with water or has a boiling point greater than the boiling point of water. Otherwise, the organic solvent may be completely removed before water during the evaporation process.
- Component (B) of the silicone composition is at least one organic solvent.
- the organic solvent can be any aprotic or dipolar aprotic organic solvent that is partially miscible or immiscible with water, does not react with the hydrolysis product, and is miscible with the hydrolysis product, component (A).
- the term “partially miscible” means that the solubility of water in the solvent is less than about 0.1 g/100 g of solvent at 25° C.
- Examples of organic solvents are as described above in the method of preparing the hydrolysis product.
- the organic solvent can be the same organic solvent used to prepare the hydrolysis product or a different organic solvent.
- the concentration of component (B) is typically from 80 to 99.9% (w/w), alternatively form 90 to 99.5% (w/w), alternatively from 95 to 99% (w/w), based on the total weight of the silicone composition.
- An organic light-emitting diode comprises:
- a substrate having a first opposing surface and a second opposing surface
- the light-emitting element comprising
- the substrate has a first opposing surface and a second opposing surface.
- the substrate can be a rigid or flexible material.
- the substrate can be transparent or nontransparent to light in the visible region of the electromagnetic spectrum.
- transparent means the particular component (e.g., substrate or electrode layer) has a percent transmittance of at least 30%, alternatively at least 60%, alternatively at least 80%, for light in the visible region ( ⁇ 400 to ⁇ 700 nm) of the electromagnetic spectrum.
- nontransparent means the component has a percent transmittance less than 30% for light in the visible region of the electromagnetic spectrum.
- substrates include, but are not limited to, semiconductor materials such as silicon, silicon having a surface layer of silicon dioxide, and gallium arsenide; quartz; fused quartz; aluminum oxide; ceramics; glass; metal foils; polyolefins such as polyethylene, polypropylene, polystyrene, and polyethyleneterephthalate; fluorocarbon polymers such as polytetrafluoroethylene and polyvinylfluoride; polyamides such as Nylon; polyimides; polyesters such as poly(methyl methacrylate) and poly(ethylene 2,6-naphthalenedicarboxylate); epoxy resins; polyethers; polycarbonates; polysulfones; and polyether sulfones.
- semiconductor materials such as silicon, silicon having a surface layer of silicon dioxide, and gallium arsenide
- quartz fused quartz
- aluminum oxide ceramics
- glass glass
- metal foils such as polyolefins such as polyethylene, polypropylene, polystyrene, and polyethylenetere
- the first electrode layer can function as an anode or cathode in the OLED.
- the first electrode layer may be transparent or nontransparent to visible light.
- the anode is typically selected from a high work-function (>4 eV) metal, alloy, or metal oxide such as indium oxide, tin oxide, zinc oxide, indium tin oxide (no), indium zinc oxide, aluminum-doped zinc oxide, nickel, and gold.
- the cathode can be a low work-function ( ⁇ 4 eV) metal such as Ca, Mg, and Al; a high work-function (>4 eV) metal, alloy, or metal oxide, as described above; or an alloy of a low-work function metal and at least one other metal having a high or low work-function, such as Mg—Al, Ag—Mg, Al—Li, In—Mg, and Al—Ca.
- Methods of depositing anode and cathode layers in the fabrication of OLEDs, such as evaporation, co-evaporation, DC magnetron sputtering, or RF sputtering, are well known in the art.
- the light-emitting element layer overlies the first electrode layer.
- the light-emitting element comprises a hole-transport/hole-injection layer and an emissiveve/electron-transport layer, wherein the hole-transport/hole-injection layer comprises a cured polysiloxane, described below.
- the orientation of the light-emitting element depends on the relative positions of the anode and cathode in the OLED.
- the hole-transport/hole-injection layer is located between the anode and the emissive/electron-transport layer, and the emissive/electron-transport layer is located between the hole-transport/hole-injection layer and the cathode.
- the thickness of the hole-transport/hole-injection layer is typically from 2 to 100 nm, alternatively from 30 to 50 nm.
- the thickness of the emissive/electron-transport layer is typically from 20 to 100 nm, alternatively from 30 to 70 nm.
- the hole-transport/hole-injection-layer comprises a cured polysiloxane prepared by applying a silicone composition to form a film and curing the film, wherein the silicone composition is as described above.
- a silicone composition is applied to the first electrode layer, a layer overlying the first electrode layer, or the emissive/electron-transport layer, depending on the configuration of the OLED, to form a film, wherein the silicone comprises components (A) and (B), described below.
- the silicone composition can be applied to the first electrode layer, a layer overlying the first electrode layer, or the emissive/electron-transport layer using conventional methods such as spin-coating, dipping, spraying, brushing, and printing.
- the film can be cured by exposing it to heat.
- the rate of cure depends on a number of factors, including the structure of the hydrolysis product and the temperature.
- Partially cured polysiloxanes generally have a higher content of silicon-bonded hydroxy (silanol) groups than more completely cured polysiloxanes.
- the extent of cure can be varied by controlling cure time and temperature.
- the silicone composition typically can be cured by exposing the composition to a temperature of from about 150° C. to about 250° C., for period from 0.1 to 1 h.
- the emissive/electron-transport layer can be any low molecular weight organic compound or organic polymer typically used as an emissive, electron-transport, electron-injection/electron-transport, or light-emitting material in OLED devices.
- Low molecular weight organic compounds suitable for use as the electron-transport layer are well known in the art, as exemplified in U.S. Pat. No. 5,952,778; U.S. Pat. No. 4,539,507; U.S. Pat. No. 4,356,429; U.S. Pat. No. 4,769,292; U.S. Pat. No. 6,048,573; and U.S. Pat. No. 5,969,474.
- low molecular weight compounds include, but are not limited to, aromatic compounds, such as anthracene, naphthalene, phenanthrene, pyrene, chrysene, and perylene; butadienes such as 1,4-diphenylbutadiene and tetraphenylbutadiene; coumarins; acridine; stilbenes such as trans-stilbene; and chelated oxinoid compounds, such as tris(8-hydroxyquinolato)aluminum(III), Alq 3 .
- aromatic compounds such as anthracene, naphthalene, phenanthrene, pyrene, chrysene, and perylene
- butadienes such as 1,4-diphenylbutadiene and tetraphenylbutadiene
- coumarins such as acridine
- stilbenes such as trans-stilbene
- chelated oxinoid compounds such as tris(8-hydroxy
- Organic polymers suitable for use as the emissive/electron-transport layer are well known in the art, as exemplified in U.S. Pat. No. 5,952,778; U.S. Pat. No. 5,247,190; U.S. Pat. No. 5,807,627; U.S. Pat. No. 6,048,573; and U.S. Pat. No. 6,255,774.
- organic polymers include, but are not limited to, poly(phenylene vinylene)s, such as poly(1,4 phenylene vinylene); poly-(2,5-dialkoxy-1,4 phenylene vinylene)s, such as poly(2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylenevinylene) (MEHPPV), poly(2-methoxy-5-(2-methylpentyloxy)-1,4-phenylenevinylene), poly(2-methoxy-5-pentyloxy-1,4-phenylenevinylene), and poly(2-methoxy-5-dodecyloxy-1,4-phenylenevinylene); poly(2,5-dialkyl-1,4 phenylene vinylene)s; poly(phenylene); poly(2,5-dialkyl-1,4 phenylene)s; poly(p-phenylene); poly(thiophene)s, such as poly(3-alkylthiophene)s,
- organic polymers also include the polyfluorene-based light-emitting polymers available from Suamtion (Tokyo, Japan), under the trademark Sumation, such as SumationTM Blue BP105 Light Emitting Polymer, SumationTM Green K2 Light Emitting Polymer, and SumationTM Red H2 Light Emitting Polymer.
- the organic polymers can be applied by conventional solvent coating techniques such as spin-coating, dipping, spraying, brushing, and printing (e.g., stencil printing and screen printing).
- the emissive/electron-transport layer can further comprise a fluorescent dye.
- fluorescent dyes suitable for use in OLED devices are well known in the art, as illustrated in U.S. Pat. No. 4,769,292.
- Examples of fluorescent dyes include, but are not limited to, coumarins; dicyanomethylenepyrans, such as 4-(dicyanomethylene)-2-methyl-6-(p-dimethylaminostyryl)4H-pyran; dicyanomethylenethiopyrans; polymethine; oxabenzanthracene; xanthene; pyrylium and thiapyrylium; cabostyril; and perylene fluorescent dyes.
- the second electrode layer can function either as an anode or cathode in the OLED.
- the second electrode layer may be transparent or nontransparent to light in the visible region. Examples of anode and cathode materials and methods for their formation are as described above for the first electrode layer.
- the OLED of the present invention can further comprise an electron-injection layer interposed between the cathode and the emissive/electron-transport layer.
- the electron-injection layer typically has a thickness of from 0.5 to 5 nm, alternatively from 1 to 3 nm.
- materials suitable for use as the electron-injection layer include, but are not limited to, alkali metal fluorides, such as lithium fluoride and cesium fluoride; and alkali metal carboxylates, such as lithium acetate and cesium acetate.
- the electron-injection layer can be formed by conventional techniques, thermal evaporation.
- the OLED of the present invention can further comprise a hole-transport layer interposed between the anode and the hole-transport/hole-injection layer.
- the hole-transport layer can be any organic compound typically used as a hole-transport, hole-injection, or hole-injection/hole-transport material in OLED devices.
- Organic compounds suitable for use as the hole-transport layer are well known in the art, as exemplified in U.S. Pat. No. 4,720,432; U.S. Pat. No. 5,593,788; U.S. Pat. No. 5,969,474; U.S. Pat. No. 4,539,507; U.S. Pat. No. 6,048,573; and U.S. Pat. No. 4,888,211.
- organic compounds include, but are not limited to, aromatic tertiary amines, such as monoarylamines, diarylamines, triarylamines, and tetraaryldiamines; hydrazones; carbazoles; triazoles; imidazoles; oxadiazoles having an amino group; polythiophenes, such as poly(3,4-ethylenedioxythiophene) poly(styrenesulfonate), which is sold under the name Baytron® P by H.C. Starck Inc.; and porhyrinic compounds, such as phthalocyanines and metal-containing phthalocyanines.
- the organic compounds can be applied by conventional thin-film preparation techniques including vacuum evaporation and sublimation.
- a first embodiment of an OLED comprises a substrate 100 having a first opposing surface 100 A and a second opposing surface 100 B, a first electrode layer 102 overlying the first opposing surface 100 A, wherein the first electrode layer 102 is an anode, a light-emitting element 104 overlying the first electrode layer 102 , wherein the light-emitting element 104 comprises a hole-transport/hole-injection layer 106 and an emissive/electron-transport layer 108 lying on the hole-transport/hole injection layer 106 , wherein the hole-transport/hole-injection layer 106 comprises a cured polysiloxane, and a second electrode layer 110 overlying the light-emitting element 104 , wherein the second electrode layer 110 is a cathode.
- a second embodiment of an OLED comprises a substrate 200 having a first opposing surface 200 A and a second opposing surface 200 B, a first electrode layer 202 overlying the first opposing surface 200 A, wherein the first electrode layer 202 is a cathode, a light-emitting element 204 overlying the first electrode layer 202 , wherein the light-emitting element 204 comprises an emissive/electron-transport layer 208 and a hole-transport/hole-injection layer 206 lying on the emissive/electron-transport layer 208 , wherein the hole-transport/hole-injection layer 206 comprises a cured polysiloxane, and a second electrode layer 210 overlying the light-emitting element 204 , wherein the second electrode layer 210 is an anode.
- the OLED of the present invention has a low turn-on voltage and high brightness.
- the hole-transport/hole-injection layer of the present invention which comprises a cured polysiloxane, exhibits high transparency and a neutral pH.
- the hydrolysis product in the silicone composition used to prepare the hole-transport/hole-injection layer is soluble in organic solvents, and the composition has good stability in the absence of moisture.
- the organic light-emitting diode of the present invention is useful as a discrete light-emitting device or as the active element of light-emitting arrays or displays, such as flat panel displays.
- OLED displays are useful in a number of devices, including watches, telephones, lap-top computers, pagers, cellular phones, digital video cameras, DVD players, and calculators.
- the substrates were immersed in an ultrasonic bath containing a solution consisting of 1% Alconox powdered cleaner (Alconox, Inc.) in water for 10 min and then rinsed with deionized water.
- the substrates were then immersed sequentially in the each of the following solvents with ultrasonic agitation for 10 min in each solvent: isopropyl alcohol, n-hexane, and toluene.
- the glass substrates were then dried under a stream of dry nitrogen. Immediately before use, the substrates were treated with oxygen plasma for 3 min.
- Calcium and aluminum films were deposited by thermal evaporation under an initial vacuum of 10 ⁇ 6 mbar using a BOC Edwards model E306A Coating System equipped with a crystal balance film thickness monitor.
- the source was prepared by placing the metal in an aluminum oxide crucible and positioning the crucible in a tungsten wire spiral, or by placing the metal directly in a tungsten basket. When multiple layers of different metals were required, the appropriate sources were placed in a turret that could be rotated for deposition of each metal. The deposition rate (0.1 to 0.3 nm per second) and the thickness of the film were monitored during the deposition process.
- Platinum Catalyst is a mixture containing 0.05% (w/w) of a platinum(0) complex of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane in anhydrous toluene.
- SumationTM Blue BP105 Light Emitting Polymer available from Sumation (Tokyo, Japan), is a polyfluorene polymer that emits light in the blue region of the visible spectrum.
- SumationTM Green K2 Light Emitting Polymer available from Sumation (Tokyo, Japan), is a polyfluorene polymer that emits light in the green region of the visible spectrum.
- SumationTM Red H2 Light Emitting Polymer available from Sumation (Tokyo, Japan), is a polyfluorene polymer that emits light in the red region of the visible spectrum.
- Example 1 The hydrosilylation reaction of Example 1 was repeated using 18.7 g of 5-allyl-2,2′-bithiophene in place of 2-allylthiophene, 10 g of anhydrous toluene, 20 g of trichlorosilane, and 150 mg of Platinum Catalyst.
- Example 1 The hydrolysis reaction of Example 1 was repeated using 5-(3-trichlorosilylpropyl)-2,2′-bithiophene in place of 2-(3-trichlorosilylpropyl)thiophene.
- Example 2 The hydrosilylation reaction of Example 1 was repeated using 4.5 g of 2-allyl-5-methylthiophene in place of 2-allylthiophene, 2.5 g of anhydrous toluene, 5.0 g of trichlorosilane, and 50 mg of Platinum Catalyst.
- Example 1 The hydrolysis reaction of Example 1 was repeated using 2-(3-trichlorosilylpropyl)-5-methylthiophene in place of 2-(3-trichlorosilylpropyl)thiophene.
- Example 1 The hydrosilylation reaction of Example 1 was repeated using 5.0 g of 5-allyl-5′-methyl-2,2′-bithiophene in place of 2-allylthiophene, 2.5 g of anhydrous toluene, 6.0 g of trichlorosilane, and 50 mg of Platinum Catalyst.
- Example 1 The hydrolysis reaction of Example 1 was repeated using 5-(3-trichlorosilylpropyl)-5′-methyl-2,2′-bithiophene in place of 2-(3-trichlorosilylpropyl)thiophene.
- Example 1 Three OLEDs were fabricated as follows: The hydrolysate of Example 1 was diluted to 0.5% (w/w) solids with MIBK. The solution was spin-coated (2000 rpm, 20 s) over an ITO-coated glass substrate, described above, using a CHEMAT Technology Model KW-4A spin-coater to form a hole-transport/hole-injection layer having a thickness of 10 nm. The substrate was heated on a hot plate at 190° C. for 0.5 h.
- the substrate was heated on a hot plate at 100° C. for 0.5 h and then allowed to cool to room temperature.
- Three cathodes were formed by depositing calcium (50 nm) and aluminum (150 nm) sequentially on top of the light-emitting polymer layer through a mask having three rectangular apertures (5 mm ⁇ 15 mm).
- a drop of epoxy adhesive (ELC 2500, Electro-Lite Corporation) was then applied on the cathodes.
- a glass slide was placed upon the epoxy and pressure was applied to spread the epoxy into a uniform layer.
- the epoxy was cured for 7 min. using a 365-nm UV lamp.
- the three OLEDs emitted a blue color light and had an average turn-on voltage at 1 cd m ⁇ 2 of about 9.6 V, average brightness at 10 V of approximately 17 cd m ⁇ 2 , and average peak luminous efficiency of 0.3 cd/A.
- OLEDs were prepared using the preceding method, but replacing SumationTM Blue BP105 with SumationTM Red H2 Light Emitting Polymer.
- the OLEDs emitted a red color and had an average turn-on voltage of 8.7 V, average brightness at 10 V of 38 cd m ⁇ 2 , and average peak luminous efficiency of 0.10 cd/A.
- OLEDs were prepared using the preceding method, but replacing SumationTM Blue BP105 with SumationTM Green K2 Light Emitting Polymer.
- the OLEDs emitted a green color and had an average turn-on voltage of 6.2 V, average brightness at 10 V of 650 cd m ⁇ 2 , and average peak luminous efficiency of 2.4 cd/A.
- OLEDS were fabricated as described in Example 5 using the hydrolysate of Example 2.
- a red-emitting device had an average turn-on voltage of 4.8 V, an average brightness at 10 V of 835 cd m ⁇ 2 , and average peak luminous efficiency of 0.35 cd/A.
- a green-emitting device had an average turn-on voltage of 4.6 V, average brightness at 10 V of 5500 cd m ⁇ 2 , and average peak luminous efficiency of 2.7 cd/A.
- a blue-emitting device had an average turn-on voltage of 5.7 V, average brightness at 10 V of 1380 cd m ⁇ 2 , and average peak luminous efficiency of 2.2 cd/A.
- OLEDS were fabricated as described in Example 5 using the hydrolysate of Example 3.
- a red-emitting device had an average turn-on voltage of 7.3 V, average brightness at 10 V of 113 cd m ⁇ 2 , and average peak luminous efficiency of 0.12 cd/A.
- a green-emitting device had an average turn-on voltage of 6.2 V, average brightness at 10 V of 977 cd m ⁇ 2 , and average peak luminous efficiency of 2.0 cd/A.
- a blue-emitting device had an average turn-on voltage of >10 V, average brightness at 10 V of 3.6 cd m ⁇ 2 , and average peak luminous efficiency of 0.11 cd/A.
- OLEDS were fabricated as described in Example 5 using the hydrolysate of Example 4.
- a red-emitting device had an average turn-on voltage of 6.7 V, average brightness at 10 V of 170 cd m ⁇ 2 , and average peak luminous efficiency of 0.31 cd/A.
- a green-emitting device had an average turn-on voltage of 5.6 V, average brightness at 10 V of 1100 cd m ⁇ 2 , and average peak luminous efficiency of 1.8 cd/A.
- a blue-emitting device had an average turn-on voltage of 6.2 V, average brightness at 10 V of 740 cd m ⁇ 2 , and average peak luminous efficiency of 1.9 cd/A.
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Abstract
A silicone composition comprising (A) a hydrolysis product prepared by reacting at least one thiophenyl-substituted silane and a cross-linking agent with water in the presence of an organic solvent to form an organic phase containing the hydrolysis product and an aqueous phase, and separating the organic phase from the aqueous phase, and (B) an organic solvent; and an organic light-emitting diode (OLED) containing a hole-transport/hole-injection layer comprising a cured polysiloxane prepared by applying the aforementioned silicone composition to form a film and curing the film.
Description
This application is a U.S. national stage filing under 35 U.S.C. §371 of PCT Application No. PCT/US09/034848 filed on 23 Feb. 2009, currently pending, which claims the benefit of U.S. Provisional Patent Application No. 61/039,455 filed 26 Mar. 2008 under 35 U.S.C. §119 (e). PCT Application No. PCT/US09/034848 and U.S. Provisional Patent Application No. 61/039,455 are hereby incorporated by reference.
The present invention relates to a silicone composition and more particularly to a silicone composition comprising (A) a hydrolysis product prepared by reacting at least one thiophenyl-substituted silane and a cross-linking agent with water in the presence of an organic solvent to form an organic phase containing the hydrolysis product and an aqueous phase, and separating the organic phase from the aqueous phase; and (B) an organic solvent. The present invention also relates to an organic light-emitting diode (OLED) containing a hole-transport/hole-injection layer comprising a cured polysiloxane prepared by applying the aforementioned silicone composition to form a film and curing the film.
Organic light-emitting diodes (OLEDs) are useful in a variety of consumer products, such as watches, telephones, lap-top computers, pagers, cellular phones, digital video cameras, DVD players, and calculators. Displays containing light-emitting diodes have numerous advantages over conventional liquid-crystal displays (LCDs). For example, OLED displays are thinner, consume less power, and are brighter than LCDs. Also, unlike LCDs, OLED displays are self-luminous and do not require backlighting. Furthermore, OLED displays have a wide viewing angle, even in bright light. As a result of these combined features, OLED displays are lighter in weight and take up less space than LCD displays.
OLEDs typically comprise a light-emitting element interposed between an anode and a cathode. The light-emitting element typically comprises a stack of thin organic layers comprising a hole-transport layer, an emissive layer, and an electron-transport layer. However, OLEDs can also contain additional layers, such as a hole-injection layer and an electron-injection layer. Furthermore, the emissive layer can contain a fluorescent dye or dopant to enhance the electroluminescent efficiency of the OLED and control color output.
Although a variety of organic polymers can be used to prepare the hole transport layer in an OLED, poly(3,4-ethylenedioxythiophene)poly(styrenesulfonate), PDOT:PSS, is a preferred hole-transport material. OLEDs containing this material typically have a low turn-on voltage and high brightness. However, a hole-transport layer comprising PDOT:PSS has many limitations including low transparency, high acidity, susceptibility to electrochemical de-doping (migration of dopant from hole-transport layer) and electrochemical decomposition. Moreover, PDOT:PSS is insoluble in organic solvents and aqueous emulsions of the polymer, used to prepare the hole-transport layer, have limited stability. Consequently, there is a need for an OLED comprising a hole-transport layer that overcomes the aforementioned limitations.
The present invention is directed to a silicone composition comprising:
(A) a hydrolysis product prepared by reacting (a) at least one thiophenyl-substituted silane having the formula Th—(CH2)m+2SiR1 nX3-n, and (b) a cross-linking agent selected from (i) at least one silane having the formula (R3 bSiX4-b), (ii) at least one organic compound having an average of at least two silyl groups per molecule, wherein the silyl groups have the formula —SiR3 cX3-c, and (iii) a mixture comprising (i) and (ii), with water in the presence of an organic solvent to form an organic phase containing the hydrolysis product and an aqueous phase, and separating the organic phase from the aqueous phase, wherein R1 is C1 to C10 hydrocarbyl free of aliphatic unsaturation, X is a hydrolysable group, Th is thiophenyl or substituted thiophenyl, R3 is C1 to C10 hydrocarbyl or —H, m is 0 to 10, n is 0, 1, or 2, b is 0 or 1, and c is 0, 1, or 2; and
(B) an organic solvent.
The present invention is also directed to an organic light-emitting diode comprising:
a substrate having a first opposing surface and a second opposing surface;
a first electrode layer overlying the first opposing surface;
a light-emitting element overlying the first electrode layer, the light-emitting element comprising
-
- an emissive/electron-transport layer, and
- a hole-transport/hole-injection layer, wherein the hole-transport/hole-injection layer comprises a cured polysiloxane prepared by applying a silicone composition to form a film and curing the film, wherein the silicone composition comprises (A) a hydrolysis product prepared by reacting (a) at least one thiophenyl-substituted silane having the formula Th—(CH2)m+2SiR1 nX3-n, and (b) a cross-linking agent selected from (i) at least one silane having the formula (R3 b SiX4-b), (ii) at least one organic compound having an average of at least two silyl groups per molecule, wherein the silyl groups have the formula —SiR3 cX3-c, and (iii) a mixture comprising (i) and (ii), with water in the presence of an organic solvent to form an organic phase containing the hydrolysis product and an aqueous phase, and separating the organic phase from the aqueous phase, wherein R1 is C1 to C10 hydrocarbyl free of aliphatic unsaturation, X is a hydrolysable group, Th is thiophenyl or substituted thiophenyl, R3 is C1 to C10 hydrocarbyl or —H, m is 0 to 10, n is 0, 1, or 2, b is 0 or 1, and c is 0, 1, or 2; and (B) an organic solvent; and
a second electrode layer overlying the light-emitting element.
The OLED of the present invention has a low turn-on voltage and high brightness. Also, the hole-transport/hole-injection layer of the present invention, which comprises a cured polysiloxane, exhibits high transparency and a neutral pH. Moreover, the hydrolysis product in the silicone composition used to prepare the hole-transport/hole-injection layer is soluble in organic solvents, and the composition has good stability in the absence of moisture.
The organic light-emitting diode of the present invention is useful as a discrete light-emitting device or as the active element of light-emitting arrays or displays, such as flat panel displays. OLED displays are useful in a number of devices, including watches, telephones, lap-top computers, pagers, cellular phones, digital video cameras, DVD players, and calculators.
These and other features, aspects, and advantages of the present invention will become better understood with reference to the following description, appended claims, and accompanying drawings.
As used herein, the term “overlying” used in reference to the position of the first electrode layer, light-emitting element, and second electrode layer relative to the designated component means the particular layer either lies directly on the component or lies above the component with one or more intermediate layers there between, provided the OLED is oriented with the substrate below the first electrode layer as shown in FIGS. 1 and 2 . For example, the term “overlying” used in reference to the position of the first electrode layer relative to the first opposing surface of the substrate in the OLED means the first electrode layer either lies directly on the surface or is separated from the surface by one or more intermediate layers.
A silicone composition according to the present invention comprises:
(A) a hydrolysis product prepared by reacting (a) at least one thiophenyl-substituted silane having the formula Th—(CH2)m+2SiR1 nX3-n, and (b) a cross-linking agent selected from (i) at least one silane having the formula (R3 bSiX4-b), (ii) at least one organic compound having an average of at least two silyl groups per molecule, wherein the silyl groups have the formula —SiR3 cX3-c, and (iii) a mixture comprising (i) and (ii), with water in the presence of an organic solvent to form an organic phase containing the hydrolysis product and an aqueous phase, and separating the organic phase from the aqueous phase, wherein R1 is C1 to C10 hydrocarbyl free of aliphatic unsaturation, X is a hydrolysable group, Th is thiophenyl or substituted thiophenyl, R3 is C1 to C10 hydrocarbyl or —H, m is 0 to 10, n is 0, 1, or 2, b is 0 or 1, and c is 0, 1, or 2; and
(B) an organic solvent.
Component (A) of the silicone composition is a hydrolysis product prepared by reacting (a) at least one thiophenyl-substituted silane having the formula Th—(CH2)m+2SiR1 nX3-n, and (b) a cross-linking agent selected from (i) at least one silane having the formula (R3 bSiX4-b), (ii) at least one organic compound having an average of at least two silyl groups per molecule, wherein the silyl groups have the formula —SiR3 cX3-c, and (iii) a mixture comprising (i) and (ii), with water in the presence of an organic solvent to form an organic phase containing the hydrolysis product and an aqueous phase, and separating the organic phase from the aqueous phase, wherein R1 is C1 to C10 hydrocarbyl free of aliphatic unsaturation, X is a hydrolysable group, Th is thiophenyl or substituted thiophenyl, R3 is C1 to C10 hydrocarbyl or —H, m is 0 to 10, n is 0, 1, or 2, b is 0 or 1, and c is 0, 1, or 2.
The thiophenyl-substituted silane (a) is at least one thiophenyl-substituted silane having the formula Th—(CH2)m+2SiR1 nX3-n, wherein R1 is C1 to C10 hydrocarbyl free of aliphatic unsaturation, X is a hydrolysable group, Th is thiophenyl or substituted thiophenyl, m is 0 to 10, and n is 0, 1, or 2. Alternatively, the subscript m has a value of from 0 to 5 or from 1 to 3.
The hydrocarbyl groups represented by R1 are free of aliphatic unsaturation and typically have from 1 to 10 carbon atoms, alternatively from 1 to 6 carbon atoms. The term “free of aliphatic unsaturation” means the group is free of aliphatic carbon-carbon double bonds and aliphatic carbon-carbon triple bonds. Acyclic hydrocarbyl groups containing at least 3 carbon atoms can have a branched or unbranched structure. Examples of hydrocarbyl groups represented by R1 include, but are not limited to, alkyl, such as methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, 1,1-dimethylethyl, pentyl, 1-methylbutyl, 1-ethylpropyl, 2-methylbutyl, 3-methylbutyl, 1,2-dimethylpropyl, 2,2-dimethylpropyl, hexyl, heptyl, octyl, nonyl, and decyl; cycloalkyl, such as cyclopentyl, cyclohexyl, and methylcyclohexyl; aryl, such as phenyl and naphthyl; alkaryl, such as tolyl and xylyl; and aralkyl, such as benzyl and phenethyl.
In the formula of the thiophenyl-substituted silane (a), X denotes a hydrolysable group. As used herein the term “hydrolysable group” means the silicon-bonded group reacts with water in either the presence or absence of a catalyst at any temperature from room temperature (˜23±2° C.) to 100° C. within several minutes, for example thirty minutes, to form a silanol (Si—OH) group. Examples of hydrolysable groups represented by X include, but are not limited to, —Cl, —Br, —OR2, —OCH2CH2OR2, CH3C(═O)O—, Et(Me)C═N—O—, CH3C(═O)N(CH3)—, and —ONH2, wherein R2 is C1 to C8 hydrocarbyl or C1 to C8 halogen-substituted hydrocarbyl, both free of aliphatic unsaturation.
The hydrocarbyl and halogen-substituted hydrocarbyl groups represented by R2 are free of aliphatic unsaturation and typically have from 1 to 8 carbon atoms, alternatively from 3 to 6 carbon atoms. Acyclic hydrocarbyl and halogen-substituted hydrocarbyl groups containing at least 3 carbon atoms can have a branched or unbranched structure. Examples of hydrocarbyl groups include, but are not limited to, unbranched and branched alkyl, such as methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, 1,1-dimethylethyl, pentyl, 1-methylbutyl, 1-ethylpropyl, 2-methylbutyl, 3-methylbutyl, 1,2-dimethylpropyl, 2,2-dimethylpropyl, hexyl, heptyl, and octyl; cycloalkyl, such as cyclopentyl, cyclohexyl, and methylcyclohexyl; phenyl; alkaryl, such as tolyl and xylyl; and aralkyl, such as benzyl and phenethyl. Examples of halogen-substituted hydrocarbyl groups include, but are not limited to, 3,3,3-trifluoropropyl, 3-chloropropyl, chlorophenyl, and dichlorophenyl.
In the formula of the thiophenyl-substituted silane (a), Th denotes a thiophenyl group or substituted thiophenyl group. As used herein, the term “thiophenyl” refers to a monovalent organic group containing a least one 5-membered heteroaromatic ring having the heteroatom sulfur and a free valence at a ring carbon atom. Examples of thiophenyl groups represented by Th include, but are not limited to, groups having the following formulae:
Furthermore, the term “substituted thiophenyl” means the thiophenyl group, described above, has a substituent replacing hydrogen on one or more positions of one or more heteroaromatic rings. Examples of substituents include, but are not limited to, alkyl such as methyl, ethyl, propyl, butyl, pentyl, and hexyl; aryl such as phenyl; and halo such as chloro and bromo.
The thiophenyl-substituted silane (a) can be a single silane or a mixture comprising two or more different thiophenyl-substituted silanes, each as described and exemplified above.
The thiophenyl-substituted silane can be prepared by reacting (i) an alkenyl-substituted thiophene having the formula Th—(CH2)mCH═CH2 with (ii) a silane having the formula HR1 nSiX3-n in the presence of (iii) a hydrosilylation catalyst and, optionally, (iv) an organic solvent, wherein R1, Th, X, m, and n are as defined and exemplified above for the thiophenyl-substituted silane.
The alkenyl-substituted thiophene (i) has the formula Th—(CH2)mCH═CH2 wherein Th and m are as defined and exemplified above for the thiophenyl-substituted silane. Examples of alkenyl-substituted thiophenes include, but are not limited to, 2-vinylthiophene, 3-vinylthiophene, 2-allylthiophene, 3-allylthiophene, 4-methyl-2-vinylthiophene, 3-methyl-2-vinylthiophene, 2-methyl-3-vinylthiophene, 5-methyl-2-vinylthiophene, 5-vinyl-2,2′-bithiophene, 3-(2-propenyl)-2,2′-bithiophene, 5-(2-propenyl)-2,2′-bithiophene, 5-vinyl-2,2′:5′,2″-terthiophene, 3′-vinyl-2,2′:5′,2″-terthiophene, and 5-ethyl-5″-vinyl-2,2′:5′,2″-terthiophene. Moreover, methods of preparing alkenyl-substituted thiophenes are well known in the art.
The silane (ii) has the formula HR1 nSiX3-n wherein R1, X, and n are as defined and exemplified above for the thiophenyl-substituted silane. Example of silanes suitable for use as silane (ii) include, but are not limited to, halosilanes such as HSiCl3, HSiBr3, HMeSiCl2, HEtSiCl2, HMeSiBr2, HEtSiBr2, HPhSiCl2, HPhSiBr2, BuHSiCl2, and i-PrHSiCl2, HMe2SiCl, HMe2SiBr, HEt2SiCl, and HEt2SiBr; alkoxysilanes such as HSi(OMe)3, HSi(OEt)3, HSi(OPr)3, HSi(OBu)3, HSi(OCH2CH2OCH3)3, HMeSi(Me)2, HMeSi(OEt)2, HMeSi(OPr)2, HMeSi(OBu)2, HPhSi(OMe)2, HPhSi(OEt)2, HMeSi(OCH2CH2OCH3)2, HPhSi(OCH2CH2OCH3)2, HMe2Si(OMe), HMe2Si(OEt), HMe2Si(OPr), HMe2Si(OBu), HPh2Si(OMe), HPh2Si(OEt), HMe2Si(OCH2CH2OCH3), HPh2Si(OCH2CH2OCH3), HEt2Si(OMe), and HEt2Si(OEt); organoacetoxysilanes such as HMeSi(OCOCH3)3, CH3CH2Si(OCOCH3)3, and CH2═CHSi(OCOCH3)3; organoiminooxysilanes such as HSi[O—N═C(CH3)CH2CH3]3; organoacetamidosilanes such as HSi[NHC(═O)CH3]3 and HSi[NHC(═O)CH3]3; amino silanes such as HSi[NH(s-C4H9)]3 and HSi(NHC6H11)3; and organoaminooxysilanes, wherein Me is methyl, Et is ethyl, Pr is propyl, Bu is butyl, and Ph is phenyl.
Methods of preparing silanes having hydrolysable groups are well known in the art; many of these compounds are commercially available.
The hydrosilylation catalyst (iii) can be any of the well-known hydrosilylation catalysts comprising a platinum group metal (i.e., platinum, rhodium, ruthenium, palladium, osmium and iridium) or a compound containing a platinum group metal. Preferably, the platinum group metal is platinum, based on its high activity in hydrosilylation reactions.
Preferred hydrosilylation catalysts include the complexes of chloroplatinic acid and certain vinyl-containing organosiloxanes disclosed by Willing in U.S. Pat. No. 3,419,593, which is hereby incorporated by reference. A preferred catalyst of this type is the reaction product of chloroplatinic acid and 1,3-diethenyl-1,1,3,3-tetramethyldisiloxane.
The organic solvent (iv) is at least one organic solvent. The organic solvent can be any aprotic or dipolar aprotic organic solvent that does not react with the alkenyl-substituted thiophene (i), the silane (ii), or the thiophenyl-substituted silane product under the conditions of the present method, and is miscible with components (i), (ii), and the thiophenyl-substituted silane.
Examples of organic solvents include, but are not limited to, saturated aliphatic hydrocarbons such as n-pentane, hexane, n-heptane, isooctane and dodecane; cycloaliphatic hydrocarbons such as cyclopentane and cyclohexane; aromatic hydrocarbons such as benzene, toluene, xylene and mesitylene; cyclic ethers such as tetrahydrofuran (THF) and dioxane; ketones such as methyl isobutyl ketone (MIBK); halogenated alkanes such as trichloroethane; and halogenated aromatic hydrocarbons such as bromobenzene and chlorobenzene. Organic solvent (iv) can be a single organic solvent or a mixture comprising two or more different organic solvents, each as defined above.
The reaction of the alkenyl-substituted thiophene (i) with the silane (ii) can be carried out in any standard reactor suitable for hydrosilylation reactions. Suitable reactors include glass and Teflon-lined glass reactors. Preferably, the reactor is equipped with a means of agitation, such as stirring. Also, preferably, the reaction is carried out in an inert atmosphere, such as nitrogen or argon, in the absence of moisture.
The alkenyl-substituted thiophene (i), silane (ii), hydrosilylation catalyst (iii), and, optionally, organic solvent (iv) can be combined in any order. Typically, the silane (ii) is added to a mixture of the alkenyl-substituted thiophene, hydrosilylation catalyst, and, optionally, organic solvent.
The reaction is typically carried out at a temperature of from 50 to 120° C., alternatively from room temperature (˜23±2° C.) to 70° C. When the temperature is less than room temperature, the rate of reaction is typically very slow.
The reaction time depends on several factors, such as the structures of the alkenyl-substituted thiophene (i) and the silane (ii), and the temperature. The time of reaction is typically from 2 to 4 h at a temperature of from 50 to 70° C. The optimum reaction time can be determined by routine experimentation using the methods set forth in the Examples section below.
The ratio of the number of moles of the silane (ii) to the number of moles of the alkenyl-substituted thiophene (i) is typically from 1 to 5, alternatively from 1 to 3, alternatively from 1 to 2. Alternatively, the alkneyl-substituted thiophene may be used in excess relative to the silane.
The concentration of hydrosilylation catalyst (iii) is sufficient to catalyze the addition reaction of the alkenyl-substituted thiophene (i) with the silane (ii). Typically, the concentration of hydrosilylation catalyst is sufficient to provide from 0.1 to 1000 ppm of a platinum group metal, alternatively from 1 to 500 ppm of a platinum group metal, alternatively from 5 to 150 ppm of a platinum group metal, based on the combined weight of the alkenyl-substituted thiophene (i) and the silane (ii). The rate of reaction is very slow below 0.1 ppm of platinum group metal. The use of more than 1000 ppm of platinum group metal results in no appreciable increase in reaction rate, and is therefore uneconomical.
The concentration of organic solvent (iv) is typically from 10 to 70% (w/w), alternatively from 20 to 50% (w/w), alternatively from 30 to 40% (w/w), based on the total weight of the reaction mixture.
The thiophenyl-substituted silane can be recovered from the reaction mixture using conventional separation/purification methods, such as distillation and chromatography.
The cross-linking agent (b) is selected from (i) at least one silane having the formula (R3 bSiX4-b), (ii) at least one organic compound having an average of at least two silyl groups per molecule, wherein the silyl groups have the formula —SiR3 cX3-c, and (iii) a mixture comprising (i) and (ii), wherein X is a hydrolysable group, R3 is C1 to C10 hydrocarbyl or —H, b is 0 or 1, and c is 0, 1, or 2.
Cross-linking agent (b)(i) is at least one silane having the formula (R3 bSiX4-b), where X, and b are as defined and exemplified above and R3 is C1 to C10 hydrocarbyl or —H. The hydrocarbyl groups represented by R3 typically have from 1 to 10 carbon atoms, alternatively from 1 to 6 carbon atoms, alternatively from 1 to 4 carbon atoms. Acyclic hydrocarbyl and halogen-substituted hydrocarbyl groups containing at least 3 carbon atoms can have a branched or unbranched structure. Examples of hydrocarbyl groups include, but are not limited to, alkyl, such as methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, 1,1-dimethylethyl, pentyl, 1-methylbutyl, 1-ethylpropyl, 2-methylbutyl, 3-methylbutyl, 1,2-dimethylpropyl, 2,2-dimethylpropyl, hexyl, heptyl, octyl, nonyl, and decyl; cycloalkyl, such as cyclopentyl, cyclohexyl, and methylcyclohexyl; aryl, such as phenyl and naphthyl; alkaryl, such as tolyl and xylyl; aralkyl, such as benzyl and phenethyl; alkenyl, such as vinyl, allyl, and propenyl; arylalkenyl, such as styryl and cinnamyl; and alkynyl, such as ethynyl and propynyl.
Examples of silanes suitable for use as cross-linking agent (b)(i), include, but are not limited to, silanes having the following formulae: SiCl4, SiBr4, Si(OMe)4, Si(OEt)4, MeSiCl3, MeSiBr3, MeSi(OMe)3, EtSiCl3, EtSiBr3, EtSi(OMe)3, MeSi(OEt)3, EtSi(OEt)3, PhSiCl3, PhSiBr3, PhSi(OMe)3, and PhSi(OEt)3.
The cross-linking agent (b)(i) can be a single silane or a mixture comprising two or more different silanes, each having the formula (R3 bSiX4-b), wherein R3, X, and b are as defined and exemplified above. Moreover, methods of preparing silanes having hydrolysable groups are well known in the art; many of these compounds are commercially available.
The cross-linking agent (b)(ii) is at least one organic compound having an average of at least two silyl groups per molecule, wherein the silyl groups have the formula —SiR3 cX3-c, wherein R3, X, and c are as defined and exemplified above. The organic compound can be a discrete compound or a polymer.
Examples of organic compounds suitable for use as cross-linking agent (b)(ii), include, but are not limited to organic compounds having the formulae R4(SiR3 cX3-c)2, R5(SiR3 cX3-c)3, and R6(SiR3 cX3-c)4, wherein R3, X, and c are as defined and exemplified above, R4 is a divalent organic group, R5 is a trivalent organic group, and R6 is a tetravalent organic group. Examples of divalent organic groups include, but are not limited to, hydrocarbylene and carbazolediyl. The hydrocarbylene groups represented by R4 typically have from 1 to 10 carbon atoms, alternatively from 1 to 6 carbon atoms, alternatively 1 to 4 carbon atoms. Examples of hydrocarbylene groups include, but are not limited to, alkylene such as methylene, ethylene, propane-1,3-diyl, 2-methylpropane-1,3-diyl, butane-1,4-diyl, butane-1,3-diyl, pentane-1,5-diyl, pentane-1,4-diyl, hexane-1,6-diyl, octane-1,8-diyl, and decane-1,10-diyl; cycloalkylene such as cyclohexane-14-diyl; and arylene such as 1,2-phenylene, 1,3-phenylene, and 1,4-phenylene. Examples of carbazolediyl groups include, but are not limited to, carbazole-1,9-diyl, carbazole-2,9-diyl, carbazole-3,9-diyl, carbazole-4,9-diyl, carbazole-2,7-diyl, carbazole-3,6-diyl, 9-methylcarbazole-2,7-diyl, 9-methylcarbazole-3,6-diyl, 9-ethylcarbazole-2,7-diyl, 9-ethylcarbazole-3,6-diyl, 9-propylcarbazole-2,7-diyl, 9-propylcarbazole-3,6-diyl, 9-butylcarbazole-2,7-diyl, 9-butylcarbazole-3,6-diyl, 9-phenylcarbazole-2,7-diyl, and 9-phenylcarbazole-3,6-diyl.
Examples of organic compounds having the formula R4(SiR3 cX3-c)2 wherein R3, R4, X, and c are as defined and exemplified above, include, but are not limited to, compounds having the following formulae: Cl3Si(CH2)2SiCl3, Cl3Si(CH2)3SiCl3, Cl3Si(CH2)4SiCl3, Cl3Si(CH2)5SiCl3, Cl3Si(CH2)6SiCl3, Cl3Si(CH2)8SiCl3, Cl3Si(CH2)10SiCl3, Cl3SiC6H4SiCl3, Br3Si(CH2)2SiBr3, Br3Si(CH2)3SiBr3, Br3Si(CH2)4SiBr3, Br3Si(CH2)5SiBr3, Br3Si(CH2)6SiBr3, Br3Si(CH2)8SiBr3, Br3Si(CH2)10SiBr3, Br3SiC6H4SiBr3, Cl2MeSi(CH2)2SiMeCl2, Cl2MeSi(CH2)3SiMeCl2, Cl2MeSi(CH2)4SiMeCl2, Cl2MeSi(CH2)5SiMeCl2, Cl2MeSi(CH2)6SiMeCl2, Cl2MeSi(CH2)8SiMeCl2, Cl2MeSi(CH2)10SiMeCl2, and Cl2MeSiC6H4SiMeCl2.
Examples of trivalent organic groups represented by R5 include, but are not limited to, propane-1,2,3-triyl, butane-1,2,3-triyl, butane-1,2,4-triyl, pentane-1,2,3-triyl, pentane-1,3,4-triyl, pentane-1,3,5-triyl, hexane-1,2,3-triyl, hexane-1,2,4-triyl, hexane-1,2,6-triyl, hexane-1,3,4-triyl, hexane-1,3,6-triyl, octane-1,2,3-triyl, octane-1,3,6-triyl, octane-1,3,8-triyl, octane-1,4,6-triyl, octane-1,4,8-triyl, cyclohexane-1,2,3-triyl, cyclohexane-1,2,4-triyl, cyclohexane-1,2,5-triyl, cyclohexane-1,3,5-triyl, benzene-1,2,4-triyl, benzene-1,2,5-triyl, and benzene-1,3,5-triyl.
Examples of organic compounds having the formula R5(SiR3 cX3-c)3 wherein R3, R5, X, and c are as defined and exemplified above, include, but are not limited to, compounds having the following formulae: Cl3SiCH2CH(SiCl3)CH2SiCl3, Cl3SiCH2CH(SiCl3)CH(SiCl3)CH3, Cl3SiCH2CH(SiCl3)CH2CH2(SiCl3), Cl3SiCH2CH2CH(SiCl3)CH2CH2SiCl3, Cl3SiCH2CH(SiCl3)CH2CH2CH2SiCl3, Cl3SiCH2CH(SiCl3)CH(SiCl3)CH2CH2CH3, Br3SiCH2CH(SiBr3)CH2SiBr3, Br3SiCH2CH(SiBr3)CH(SiBr3)CH3, Br3SiCH2CH(SiBr3)CH2CH2(SiBr3), Br3SiCH2CH2CH(SiBr3)CH2CH2SiBr3, Br3SiCH2CH(SiBr3)CH2CH2CH2SiBr3, Br3SiCH2CH(SiBr3)CH(SiBr3)CH2CH2CH3, (MeO)3SiCH2CH(Si(OMe)3)CH2Si(OMe)3, (MeO)3SiCH2CH(Si(OMe)3)CH(Si(OMe)3)CH3; (MeO)3SiCH2CH(Si(OMe)3)CH2CH2(Si(OMe)3), (MeO)3SiCH2CH2CH(Si(OMe)3)CH2CH2Si(OMe)3, (MeO)3SiCH2CH(Si(OMe)3)CH2CH2CH2Si(OMe)3, and (MeO)3SiCH2CH(Si(OMe)3)CH(Si(OMe)3)CH2CH2CH3.
Examples of tetravalent organic groups represented by R6 include, but are not limited to, butane-1,2,3,4-tetrayl, pentane-1,2,3,4-tetrayl, pentane-1,2,3,5-tetrayl, pentane-1,2,4,5-tetrayl, hexane-1,2,3,4-tetrayl, hexane-1,2,3,5-tetrayl, hexane-1,2,3,6-tetrayl, hexane-1,3,4,5-tetrayl, hexane-1,3,4,6-tetrayl, octane-1,2,3,4-tetrayl, octane-1,2,3,6-tetrayl, octane-1,2,3,8-tetrayl, octane-1,3,4,6-tetrayl, octane-1,3,4,8-tetrayl, cyclohexane-1,2,3,4-tetrayl, cyclohexane-1,2,3,5-tetrayl, cyclohexane-1,2,4,5-tetrayl, phenylene-1,2,3,4-tetrayl, phenylene-1,2,3,5-tetrayl, and phenylene-1,2,4,5-tetrayl.
Examples of organic compounds having the formula R6(SiR3 cX3-c)4 wherein R3, R6, X, and c are as defined and exemplified above, include, but are not limited to, compounds having the following formulae: Cl3SiCH2CH(SiCl3)CH(SiCl3)CH2(SiCl3), Cl3SiCH2CH2(SiCl3)CH(SiCl3)CH(SiCl3)CH3, Cl3SiCH2CH2(SiCl3)CH(SiCl3)CH2CH2SiCl3; Cl3SiCH2CH2(SiCl3)CH2CH(SiCl3)CH2SiCl3, Cl3SiCH2CH(SiCl3)CH(SiCl3)CH(SiCl3)CH2CH3, Cl3SiCH2CH(SiCl3)CH(SiCl3)CH2CH(SiCl3)CH3, Cl3SiCH2CH(SiCl3)CH(SiCl3)CH2CH2CH2SiCl3, Cl3SiCH2CH(SiCl3)CH2CH(SiCl3)CH(SiCl3)CH3, Cl3SiCH2CH(SiCl3)CH2CH2CH(SiCl3)CH2SiCl3, Br3SiCH2CH(SiBr3)CH(SiBr3)CH2(SiBr3), Br3SiCH2CH2(SiBr3)CH(SiBr3)CH(SiBr3)CH3, Br3SiCH2CH2(SiBr3)CH(SiBr3)CH2CH2SiBr3; Br3SiCH2CH2(SiBr3)CH2CH(SiBr3)CH2SiBr3; Br3SiCH2CH(SiBr3)CH(SiBr3)CH(SiBr3)CH2CH3, Br3SiCH2CH(SiBr3)CH(SiBr3)CH2CH(SiBr3)CH3, Br3SiCH2CH(SiBr3)CH(SiBr3)CH2CH2CH2SiBr3, Br3SiCH2CH(SiBr3)CH2CH(SiBr3)CH(SiBr3)CH3, Br3SiCH2CH(SiBr3)CH2CH2CH(SiBr3)CH2SiBr3, (MeO)3SiCH2CH(Si(OMe)3)CH(Si(OMe)3)CH2(Si(OMe)3), (MeO)3SiCH2CH2(Si(OMe)3)CH(Si(OMe)3)CH(Si(OMe)3)CH3, (MeO)3SiCH2CH2(Si(OMe)3)CH(Si(OMe)3)CH2CH2Si(OMe)3, (MeO)3SiCH2CH2(Si(OMe)3)CH2CH(Si(OMe)3)CH2Si(OMe)3, (MeO)3SiCH2CH(Si(OMe)3)CH(Si(OMe)3)CH(Si(OMe)3)CH2CH3, (MeO)3SiCH2CH(Si(OMe)3)CH(Si(OMe)3)CH2CH(Si(OMe)3)CH3, (MeO)3SiCH2CH(Si(OMe)3)CH(Si(OMe)3)CH2CH2CH2Si(OMe)3; (MeO)3SiCH2CH(Si(OMe)3)CH2CH(Si(OMe)3)CH(Si(OMe)3)CH3, and (MeO)3SiCH2CH(Si(OMe)3)CH2CH2CH(Si(OMe)3)CH2Si(OMe)3.
The organic compound can also be a polymer having an average of at least two silyl groups per molecule. The polymer can be a homopolymer containing identical repeat units or a copolymer containing two or more different repeat units. In a copolymer, the units can be in any order. For example, the polymer can be a random, alternating, or block copolymer.
The polymer typically has a number-average molecular weight of from 500 to 100,000, alternatively from 1000 to 10,000, alternatively from 2000 to 5000.
Examples of polymers include, but are not limited to, polymers having the following formulae: —[CH(OCH2CH2SiCl3)CH2]—, —[CH(OCH2CH2CH2SiCl3)CH2]—, —[CH(C6H4OCH2CH2SiCl3)CH2]—, —[CH(C6H4OCH2CH2CH2SiCl3)CH2]—, —[Si(CH3)(CH2CH2SiCl3)O]—, —[CH(OCH2CH2SiBr3)CH2]—; —[CH(OCH2CH2CH2SiBr3)CH2]—; —[CH(C6H4OCH2CH2SiBr3)CH2]—, —[CH(C6H4OCH2CH2CH2SiBr3)CH2]—, —[Si(CH3)(CH2CH2SiBr3)O]—, —[CH(OCH2CH2Si(OMe)3)CH2]—, —[CH(OCH2CH2CH2Si(OMe)3)CH2]—, —[CH(C6H4OCH2CH2Si(OMe)3)CH2]—, —[CH(C6H4OCH2CH2CH2Si(OMe)3)CH2]—, and —[Si(CH3)(CH2CH2Si(OMe)3)O]—, where the polymer has a number-average molecular weight of from 500 to 100,000.
The cross-linking agent (b)(ii) can be a single organic compound or a mixture comprising two or more different organic compounds, each as described and exemplified above. Moreover, methods of preparing organic compounds having silyl groups are well known in the art.
The cross-linking agent (b)(iii) is a mixture comprising (b)(i) and (b)(ii), each as described and exemplified above.
The thiophenyl-substituted silane and cross-linking agent are reacted with water in the presence of an organic solvent. The organic solvent can be any aprotic or dipolar aprotic organic solvent that is partially miscible or immiscible with water, does not react with the thiophenyl-substituted silane (a), the cross-linking agent (b), or the hydrolysis product under the conditions of the present method, and is miscible with the thiophenyl-substituted silane (a), the cross-linking agent (b), and the hydrolysis product. As used herein, the term “partially miscible” means that the solubility of water in the solvent is less than about 0.1 g/100 g of solvent at 25° C.
Examples of organic solvents include, but are not limited to, saturated aliphatic hydrocarbons such as n-pentane, hexane, n-heptane, isooctane and dodecane; cycloaliphatic hydrocarbons such as cyclopentane and cyclohexane; aromatic hydrocarbons such as benzene, toluene, xylene and mesitylene; cyclic ethers such as tetrahydrofuran (THF) and dioxane; ketones such as methyl isobutyl ketone (MIBK); halogenated alkanes such as trichloroethane; and halogenated aromatic hydrocarbons such as bromobenzene and chlorobenzene. The organic solvent can be a single organic solvent or a mixture comprising two or more different organic solvents, each as described above.
The reaction of the thiophenyl-substituted silane (a) and the cross-linking agent (b) with water can be carried out in any standard reactor suitable for contacting organohalosilanes with water. Suitable reactors include glass and Teflon-lined glass reactors. Preferably, the reactor is equipped with a means of agitation, such as stirring.
The thiophenyl-substituted silane (a), the cross-linking agent (b), and water are typically combined by adding the water to a mixture of components (a), (b), and the organic solvent. Reverse addition, i.e., addition of the thiophenyl-substituted silane (a) and the cross-linking agent (b) to water is also possible. However, reverse addition may result in formation of a gel.
The rate of addition of water to the thiophenyl-substituted silane (a) and the cross-linking agent (b) is typically from 0.1 to 1 mL/min. for a 1000-mL reaction vessel equipped with an efficient means of stirring. When the rate of addition is too slow, the reaction time is unnecessarily prolonged. When the rate of addition is too fast, the reaction mixture may form a gel.
The reaction of the thiophenyl-substituted silane (a) and the cross-linking agent (b) with water is typically carried out at a temperature of from −78 to 25° C., alternatively from −78 to 0° C., alternatively from −78 to −50° C.
The reaction time depends on several factors, including the structures of the thiophenyl-substituted silane (a) and the cross-linking agent (b), and the temperature. The reaction is typically carried out for an amount of time sufficient to complete hydrolysis of the thiophenyl-substituted silane (a) and the cross-linking agent (b). As used herein, the term “to complete hydrolysis” means that at least 85 mol % of the silicon-bonded groups —X originally present in the thiophenyl-substituted silane (a) and the cross-linking agent (b) are converted to silicon-bonded hydroxy groups. For example, the reaction time is typically from 10 to 240 min., alternatively from 30 to 180 min., alternatively from 60 to 120 min., at a temperature of from −78 to −50° C. The optimum reaction time can be determined by routine experimentation using the methods set forth in the Examples section below.
The concentration of the thiophenyl-substituted silane (a) is typically from 50 to 95 mol %, alternatively from 60 to 90 mol %, alternatively from 70 to 80 mol %, based on the sum of the number of moles of components (a) and (b).
The concentration of the organic solvent is typically from 50 to 90% (w/w), alternatively from 60 to 80% (w/w), alternatively from 70 to 75% (w/w), based on the total weight of the reaction mixture.
The concentration of water in the reaction mixture is typically sufficient to effect hydrolysis of the thiophenyl-substituted silane (a) and the cross-linking agent (b). For example, the concentration of water is typically such that the ratio of the number of moles of water to the sum of the number of moles of the silicon-bonded groups —X in the thiophenyl-substituted silane (a) and the cross-linking agent (b) is from 1 to 10, alternatively from 2 to 5.
When the thiophenyl-substituted silane (a) and the cross-linking agent (b) contain hydrolysable groups that do not react with water to form an acid or a base, the reaction mixture can further comprise at least one hydrolysis catalyst. The hydrolysis catalyst can be any acid catalyst or basic catalyst typically used to catalyze the hydrolysis of organosilanes containing hydrolysable groups that do not react with water to form an acid or a base.
Examples of acid catalysts include, but are not limited to, inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, and hydrofluoric acid; and organic acids such as acetic acid, oxalic acid, and trifluoroacetic acid. The acid catalyst can be a single acid catalyst or a mixture comprising two or more different acid catalysts.
Examples of alkali catalysts include, but are not limited to, inorganic bases such as ammonium hydroxide; and organic bases such as tetramethylammonium hydroxide, tetrabutylammonium hydroxide, and tetrabutylphosphonium hydroxide. The alkali catalyst can be a single alkali catalyst or a mixture comprising two or more different alkali catalysts.
In the method of preparing the hydrolysis product, the organic phase containing the hydrolysis product is separated from the aqueous phase. This separation can be achieved using conventional methods. For example, the organic phase can be separated from the aqueous phase by discontinuing agitation of the mixture, allowing the mixture to separate into two layers, an organic phase and an aqueous phase, and removing the organic phase containing the hydrolysis product. The organic phase is typically washed with water until the wash has a neutral pH. Residual water can be removed from the organic phase using conventional methods such as evaporation under reduced pressure. In this case, the organic solvent typically either forms a minimum boiling azeotrope with water or has a boiling point greater than the boiling point of water. Otherwise, the organic solvent may be completely removed before water during the evaporation process.
Component (B) of the silicone composition is at least one organic solvent. The organic solvent can be any aprotic or dipolar aprotic organic solvent that is partially miscible or immiscible with water, does not react with the hydrolysis product, and is miscible with the hydrolysis product, component (A). As used herein, the term “partially miscible” means that the solubility of water in the solvent is less than about 0.1 g/100 g of solvent at 25° C. Examples of organic solvents are as described above in the method of preparing the hydrolysis product. The organic solvent can be the same organic solvent used to prepare the hydrolysis product or a different organic solvent.
The concentration of component (B) is typically from 80 to 99.9% (w/w), alternatively form 90 to 99.5% (w/w), alternatively from 95 to 99% (w/w), based on the total weight of the silicone composition.
An organic light-emitting diode according to the present invention comprises:
a substrate having a first opposing surface and a second opposing surface;
a first electrode layer overlying the first opposing surface;
a light-emitting element overlying the first electrode layer, the light-emitting element comprising
-
- an emissive/electron-transport layer, and
- a hole-transport/hole-injection layer, wherein the hole-transport/hole-injection layer comprises a cured polysiloxane prepared by applying a silicone composition to form a film and curing the film, wherein the silicone composition comprises (A) a hydrolysis product prepared by reacting (a) at least one thiophenyl-substituted silane having the formula Th—(CH2)m+2SiR1 nX3-n, and (b) a cross-linking agent selected from (i) at least one silane having the formula (R3 bSiX4-b), (ii) at least one organic compound having an average of at least two silyl groups per molecule, wherein the silyl groups have the formula —SiR3 cX3-c, and (iii) a mixture comprising (i) and (ii), with water in the presence of an organic solvent to form an organic phase containing the hydrolysis product and an aqueous phase, and separating the organic phase from the aqueous phase, wherein R1 is C1 to C10 hydrocarbyl free of aliphatic unsaturation, X is a hydrolysable group, Th is thiophenyl or substituted thiophenyl, R3 is C1 to C10 hydrocarbyl or —H, m is 0 to 10, n is 0, 1, or 2, b is 0 or 1, and c is 0, 1, or 2; and (B) an organic solvent; and
a second electrode layer overlying the light-emitting element.
The substrate has a first opposing surface and a second opposing surface. Also, the substrate can be a rigid or flexible material. Further, the substrate can be transparent or nontransparent to light in the visible region of the electromagnetic spectrum. As used herein, the term “transparent” means the particular component (e.g., substrate or electrode layer) has a percent transmittance of at least 30%, alternatively at least 60%, alternatively at least 80%, for light in the visible region (˜400 to ˜700 nm) of the electromagnetic spectrum. Also, as used herein, the term “nontransparent” means the component has a percent transmittance less than 30% for light in the visible region of the electromagnetic spectrum.
Examples of substrates include, but are not limited to, semiconductor materials such as silicon, silicon having a surface layer of silicon dioxide, and gallium arsenide; quartz; fused quartz; aluminum oxide; ceramics; glass; metal foils; polyolefins such as polyethylene, polypropylene, polystyrene, and polyethyleneterephthalate; fluorocarbon polymers such as polytetrafluoroethylene and polyvinylfluoride; polyamides such as Nylon; polyimides; polyesters such as poly(methyl methacrylate) and poly(ethylene 2,6-naphthalenedicarboxylate); epoxy resins; polyethers; polycarbonates; polysulfones; and polyether sulfones.
The first electrode layer can function as an anode or cathode in the OLED. The first electrode layer may be transparent or nontransparent to visible light. The anode is typically selected from a high work-function (>4 eV) metal, alloy, or metal oxide such as indium oxide, tin oxide, zinc oxide, indium tin oxide (no), indium zinc oxide, aluminum-doped zinc oxide, nickel, and gold. The cathode can be a low work-function (<4 eV) metal such as Ca, Mg, and Al; a high work-function (>4 eV) metal, alloy, or metal oxide, as described above; or an alloy of a low-work function metal and at least one other metal having a high or low work-function, such as Mg—Al, Ag—Mg, Al—Li, In—Mg, and Al—Ca. Methods of depositing anode and cathode layers in the fabrication of OLEDs, such as evaporation, co-evaporation, DC magnetron sputtering, or RF sputtering, are well known in the art.
The light-emitting element layer overlies the first electrode layer. The light-emitting element comprises a hole-transport/hole-injection layer and an emissiveve/electron-transport layer, wherein the hole-transport/hole-injection layer comprises a cured polysiloxane, described below. The orientation of the light-emitting element depends on the relative positions of the anode and cathode in the OLED. The hole-transport/hole-injection layer is located between the anode and the emissive/electron-transport layer, and the emissive/electron-transport layer is located between the hole-transport/hole-injection layer and the cathode. The thickness of the hole-transport/hole-injection layer is typically from 2 to 100 nm, alternatively from 30 to 50 nm. The thickness of the emissive/electron-transport layer is typically from 20 to 100 nm, alternatively from 30 to 70 nm.
The hole-transport/hole-injection-layer comprises a cured polysiloxane prepared by applying a silicone composition to form a film and curing the film, wherein the silicone composition is as described above.
A silicone composition is applied to the first electrode layer, a layer overlying the first electrode layer, or the emissive/electron-transport layer, depending on the configuration of the OLED, to form a film, wherein the silicone comprises components (A) and (B), described below.
The silicone composition can be applied to the first electrode layer, a layer overlying the first electrode layer, or the emissive/electron-transport layer using conventional methods such as spin-coating, dipping, spraying, brushing, and printing.
The film can be cured by exposing it to heat. The rate of cure depends on a number of factors, including the structure of the hydrolysis product and the temperature. Partially cured polysiloxanes generally have a higher content of silicon-bonded hydroxy (silanol) groups than more completely cured polysiloxanes. The extent of cure can be varied by controlling cure time and temperature. For example, the silicone composition typically can be cured by exposing the composition to a temperature of from about 150° C. to about 250° C., for period from 0.1 to 1 h.
The emissive/electron-transport layer can be any low molecular weight organic compound or organic polymer typically used as an emissive, electron-transport, electron-injection/electron-transport, or light-emitting material in OLED devices. Low molecular weight organic compounds suitable for use as the electron-transport layer are well known in the art, as exemplified in U.S. Pat. No. 5,952,778; U.S. Pat. No. 4,539,507; U.S. Pat. No. 4,356,429; U.S. Pat. No. 4,769,292; U.S. Pat. No. 6,048,573; and U.S. Pat. No. 5,969,474. Examples of low molecular weight compounds include, but are not limited to, aromatic compounds, such as anthracene, naphthalene, phenanthrene, pyrene, chrysene, and perylene; butadienes such as 1,4-diphenylbutadiene and tetraphenylbutadiene; coumarins; acridine; stilbenes such as trans-stilbene; and chelated oxinoid compounds, such as tris(8-hydroxyquinolato)aluminum(III), Alq3. These low molecular weight organic compounds may be deposited by standard thin-film preparation techniques including vacuum evaporation and sublimation.
Organic polymers suitable for use as the emissive/electron-transport layer are well known in the art, as exemplified in U.S. Pat. No. 5,952,778; U.S. Pat. No. 5,247,190; U.S. Pat. No. 5,807,627; U.S. Pat. No. 6,048,573; and U.S. Pat. No. 6,255,774. Examples of organic polymers include, but are not limited to, poly(phenylene vinylene)s, such as poly(1,4 phenylene vinylene); poly-(2,5-dialkoxy-1,4 phenylene vinylene)s, such as poly(2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylenevinylene) (MEHPPV), poly(2-methoxy-5-(2-methylpentyloxy)-1,4-phenylenevinylene), poly(2-methoxy-5-pentyloxy-1,4-phenylenevinylene), and poly(2-methoxy-5-dodecyloxy-1,4-phenylenevinylene); poly(2,5-dialkyl-1,4 phenylene vinylene)s; poly(phenylene); poly(2,5-dialkyl-1,4 phenylene)s; poly(p-phenylene); poly(thiophene)s, such as poly(3-alkylthiophene)s; poly(alkylthienylene)s, such as poly(3-dodecylthienylene); poly(fluorene)s, such as poly(9,9-dialkyl fluorine)s; and polyanilines. Examples of organic polymers also include the polyfluorene-based light-emitting polymers available from Suamtion (Tokyo, Japan), under the trademark Sumation, such as Sumation™ Blue BP105 Light Emitting Polymer, Sumation™ Green K2 Light Emitting Polymer, and Sumation™ Red H2 Light Emitting Polymer. The organic polymers can be applied by conventional solvent coating techniques such as spin-coating, dipping, spraying, brushing, and printing (e.g., stencil printing and screen printing).
The emissive/electron-transport layer can further comprise a fluorescent dye. Fluorescent dyes suitable for use in OLED devices are well known in the art, as illustrated in U.S. Pat. No. 4,769,292. Examples of fluorescent dyes include, but are not limited to, coumarins; dicyanomethylenepyrans, such as 4-(dicyanomethylene)-2-methyl-6-(p-dimethylaminostyryl)4H-pyran; dicyanomethylenethiopyrans; polymethine; oxabenzanthracene; xanthene; pyrylium and thiapyrylium; cabostyril; and perylene fluorescent dyes.
The second electrode layer can function either as an anode or cathode in the OLED. The second electrode layer may be transparent or nontransparent to light in the visible region. Examples of anode and cathode materials and methods for their formation are as described above for the first electrode layer.
The OLED of the present invention can further comprise an electron-injection layer interposed between the cathode and the emissive/electron-transport layer. The electron-injection layer typically has a thickness of from 0.5 to 5 nm, alternatively from 1 to 3 nm. Examples of materials suitable for use as the electron-injection layer include, but are not limited to, alkali metal fluorides, such as lithium fluoride and cesium fluoride; and alkali metal carboxylates, such as lithium acetate and cesium acetate. The electron-injection layer can be formed by conventional techniques, thermal evaporation.
The OLED of the present invention can further comprise a hole-transport layer interposed between the anode and the hole-transport/hole-injection layer. The hole-transport layer can be any organic compound typically used as a hole-transport, hole-injection, or hole-injection/hole-transport material in OLED devices. Organic compounds suitable for use as the hole-transport layer are well known in the art, as exemplified in U.S. Pat. No. 4,720,432; U.S. Pat. No. 5,593,788; U.S. Pat. No. 5,969,474; U.S. Pat. No. 4,539,507; U.S. Pat. No. 6,048,573; and U.S. Pat. No. 4,888,211. Examples of organic compounds include, but are not limited to, aromatic tertiary amines, such as monoarylamines, diarylamines, triarylamines, and tetraaryldiamines; hydrazones; carbazoles; triazoles; imidazoles; oxadiazoles having an amino group; polythiophenes, such as poly(3,4-ethylenedioxythiophene) poly(styrenesulfonate), which is sold under the name Baytron® P by H.C. Starck Inc.; and porhyrinic compounds, such as phthalocyanines and metal-containing phthalocyanines. The organic compounds can be applied by conventional thin-film preparation techniques including vacuum evaporation and sublimation.
As shown in FIG. 1 , a first embodiment of an OLED according to the present invention comprises a substrate 100 having a first opposing surface 100A and a second opposing surface 100B, a first electrode layer 102 overlying the first opposing surface 100A, wherein the first electrode layer 102 is an anode, a light-emitting element 104 overlying the first electrode layer 102, wherein the light-emitting element 104 comprises a hole-transport/hole-injection layer 106 and an emissive/electron-transport layer 108 lying on the hole-transport/hole injection layer 106, wherein the hole-transport/hole-injection layer 106 comprises a cured polysiloxane, and a second electrode layer 110 overlying the light-emitting element 104, wherein the second electrode layer 110 is a cathode.
As shown in FIG. 2 , a second embodiment of an OLED according to the present invention comprises a substrate 200 having a first opposing surface 200A and a second opposing surface 200B, a first electrode layer 202 overlying the first opposing surface 200A, wherein the first electrode layer 202 is a cathode, a light-emitting element 204 overlying the first electrode layer 202, wherein the light-emitting element 204 comprises an emissive/electron-transport layer 208 and a hole-transport/hole-injection layer 206 lying on the emissive/electron-transport layer 208, wherein the hole-transport/hole-injection layer 206 comprises a cured polysiloxane, and a second electrode layer 210 overlying the light-emitting element 204, wherein the second electrode layer 210 is an anode.
The OLED of the present invention has a low turn-on voltage and high brightness. Also, the hole-transport/hole-injection layer of the present invention, which comprises a cured polysiloxane, exhibits high transparency and a neutral pH. Moreover, the hydrolysis product in the silicone composition used to prepare the hole-transport/hole-injection layer is soluble in organic solvents, and the composition has good stability in the absence of moisture.
The organic light-emitting diode of the present invention is useful as a discrete light-emitting device or as the active element of light-emitting arrays or displays, such as flat panel displays. OLED displays are useful in a number of devices, including watches, telephones, lap-top computers, pagers, cellular phones, digital video cameras, DVD players, and calculators.
The following examples are presented to better illustrate the silicone composition and OLED of the present invention, but are not to be considered as limiting the invention, which is delineated in the appended claims. Unless otherwise noted, all parts and percentages reported in the examples are by weight. The following methods and materials were employed in the examples:
NMR Spectra
Nuclear magnetic resonance spectra (1H NMR) of thiophenyl-substituted silanes in CDCl3 were obtained using a Varian 300 MHz NMR spectrometer.
Preparation of Ito-Coated Glass Substrates
Patterned ITO-coated glass substrates measuring 200 mm×200 mm×0.2 mm and having a surface resistance of 15 Ω/square were purchased from Geomatic Co., Ltd. Each substrate has a pattern of three rectangular-shaped layers of ITO (thickness=1500±150 Å) on silicon dioxide (thickness=150±100 Å), each oriented parallel to one another. The substrates were cut into 25-mm square samples.
The substrates were immersed in an ultrasonic bath containing a solution consisting of 1% Alconox powdered cleaner (Alconox, Inc.) in water for 10 min and then rinsed with deionized water. The substrates were then immersed sequentially in the each of the following solvents with ultrasonic agitation for 10 min in each solvent: isopropyl alcohol, n-hexane, and toluene. The glass substrates were then dried under a stream of dry nitrogen. Immediately before use, the substrates were treated with oxygen plasma for 3 min.
Deposition of Ca and Al Films in OLEDs
Calcium and aluminum films were deposited by thermal evaporation under an initial vacuum of 10−6 mbar using a BOC Edwards model E306A Coating System equipped with a crystal balance film thickness monitor. The source was prepared by placing the metal in an aluminum oxide crucible and positioning the crucible in a tungsten wire spiral, or by placing the metal directly in a tungsten basket. When multiple layers of different metals were required, the appropriate sources were placed in a turret that could be rotated for deposition of each metal. The deposition rate (0.1 to 0.3 nm per second) and the thickness of the film were monitored during the deposition process.
Platinum Catalyst is a mixture containing 0.05% (w/w) of a platinum(0) complex of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane in anhydrous toluene.
Sumation™ Blue BP105 Light Emitting Polymer, available from Sumation (Tokyo, Japan), is a polyfluorene polymer that emits light in the blue region of the visible spectrum.
Sumation™ Green K2 Light Emitting Polymer, available from Sumation (Tokyo, Japan), is a polyfluorene polymer that emits light in the green region of the visible spectrum.
Sumation™ Red H2 Light Emitting Polymer, available from Sumation (Tokyo, Japan), is a polyfluorene polymer that emits light in the red region of the visible spectrum.
2-Allylthiophene (25 g), 13 g of anhydrous toluene (13 g), and 250 mg of Platinum Catalyst were combined under nitrogen in a three-neck flask equipped with a reflux condenser and a dropping funnel. Then, 30 g of trichlorosilane was added drop-wise to the mixture. Upon completion of the addition, the mixture was heated to 60° C. and maintained at that temperature for 2 h. Then, the mixture was distilled at 150° C. and 0.02 ton to give 2-(3-trichlorosilylpropyl)thiophene as a colorless liquid: 1H NMR (CDCl3) δ 7.16 (dd, 1H, J=5.1, 0.9 Hz); 6.95 (dd, 1H, J=4.8, 3.3 Hz); 6.83 (m, 1H); 2.96 (t, 2H, J=7.2 Hz); 1.98 (m, 2H); 1.46 (m, 2H).
2-(3-Trichlorosilylpropyl)thiophene (5.0 g) and 50 g of methyl isobutyl ketone were combined in a flask. Then, 400 mg of silicon tetrachloride and 430 mg of 1,8-bis(trichlorosilyl)octane were added to the solution. The resulting mixture was cooled at −78° C. for 1 h. Next, 10 g of water was added to the mixture during a period of 1 h. When the addition of water was complete, the mixture was allowed to slowly warm to room temperature. The mixture was washed with water until the washings were no longer acidic. Residual water was removed in vacuo and the mixture was filtered using a 0.1 μm PTFE syringe filter.
The hydrosilylation reaction of Example 1 was repeated using 18.7 g of 5-allyl-2,2′-bithiophene in place of 2-allylthiophene, 10 g of anhydrous toluene, 20 g of trichlorosilane, and 150 mg of Platinum Catalyst. 5-(3-Trichlorosilylpropyl)-2,2′-bithiophene was obtained as a colorless liquid: 1H NMR (CDCl3) δ 7.20 (dd, 1H, J=5.1, 1.2 Hz); 7.14 (dd, 1H, J=3.6, 0.9 Hz); 7.02 (m, 2H); 6.74 (d, 1H, J=3.6 Hz); 2.93 (t, 2H, J=7.2 Hz); 1.99 (m, 2H); 1.49 (m, 2H).
The hydrolysis reaction of Example 1 was repeated using 5-(3-trichlorosilylpropyl)-2,2′-bithiophene in place of 2-(3-trichlorosilylpropyl)thiophene.
The hydrosilylation reaction of Example 1 was repeated using 4.5 g of 2-allyl-5-methylthiophene in place of 2-allylthiophene, 2.5 g of anhydrous toluene, 5.0 g of trichlorosilane, and 50 mg of Platinum Catalyst. 2-(3-Trichlorosilylpropyl)-5-methylthiophene was obtained as a colorless liquid: 1H NMR (CDCl3) δ 6.60 (m, 2H); 2.88 (t, 2H, J=7.2 Hz); 2.47 (s, 3H); 1.95 (m, 2H); 1.47 (m, 2H).
The hydrolysis reaction of Example 1 was repeated using 2-(3-trichlorosilylpropyl)-5-methylthiophene in place of 2-(3-trichlorosilylpropyl)thiophene.
The hydrosilylation reaction of Example 1 was repeated using 5.0 g of 5-allyl-5′-methyl-2,2′-bithiophene in place of 2-allylthiophene, 2.5 g of anhydrous toluene, 6.0 g of trichlorosilane, and 50 mg of Platinum Catalyst. 5-(3-Trichlorosilylpropyl)-5′-methyl-2,2′-bithiophene was obtained as a colorless liquid: 1H NMR (CDCl3) δ 6.92 (d, 1H, J=3.6 Hz); 6.91 (d, 1H, J=2.7 Hz); 6.70 (d, 2H, J=3.6 Hz); 6.65 (m, 1H); 2.91 (t, 2H, J=7.2 Hz); 2.48 (d, 3H, J=1.2 Hz); 1.97 (m, 2H); 1.47 (m, 2H).
The hydrolysis reaction of Example 1 was repeated using 5-(3-trichlorosilylpropyl)-5′-methyl-2,2′-bithiophene in place of 2-(3-trichlorosilylpropyl)thiophene.
Three OLEDs were fabricated as follows: The hydrolysate of Example 1 was diluted to 0.5% (w/w) solids with MIBK. The solution was spin-coated (2000 rpm, 20 s) over an ITO-coated glass substrate, described above, using a CHEMAT Technology Model KW-4A spin-coater to form a hole-transport/hole-injection layer having a thickness of 10 nm. The substrate was heated on a hot plate at 190° C. for 0.5 h. A solution consisting of 1.5 wt % of Sumation™ Blue BP105 Light-Emitting Polymer in xylene was then spin-coated (2250 rpm, 30 second) over the hole-transport/hole-injection layer to form an emissive/electron-transport layer having a thickness of about 70 nm. The substrate was heated on a hot plate at 100° C. for 0.5 h and then allowed to cool to room temperature. Three cathodes were formed by depositing calcium (50 nm) and aluminum (150 nm) sequentially on top of the light-emitting polymer layer through a mask having three rectangular apertures (5 mm×15 mm). A drop of epoxy adhesive (ELC 2500, Electro-Lite Corporation) was then applied on the cathodes. A glass slide was placed upon the epoxy and pressure was applied to spread the epoxy into a uniform layer. The epoxy was cured for 7 min. using a 365-nm UV lamp. The three OLEDs emitted a blue color light and had an average turn-on voltage at 1 cd m−2 of about 9.6 V, average brightness at 10 V of approximately 17 cd m−2, and average peak luminous efficiency of 0.3 cd/A.
Three OLEDs were prepared using the preceding method, but replacing Sumation™ Blue BP105 with Sumation™ Red H2 Light Emitting Polymer. The OLEDs emitted a red color and had an average turn-on voltage of 8.7 V, average brightness at 10 V of 38 cd m−2, and average peak luminous efficiency of 0.10 cd/A.
Finally, three OLEDs were prepared using the preceding method, but replacing Sumation™ Blue BP105 with Sumation™ Green K2 Light Emitting Polymer. The OLEDs emitted a green color and had an average turn-on voltage of 6.2 V, average brightness at 10 V of 650 cd m−2, and average peak luminous efficiency of 2.4 cd/A.
OLEDS were fabricated as described in Example 5 using the hydrolysate of Example 2. A red-emitting device had an average turn-on voltage of 4.8 V, an average brightness at 10 V of 835 cd m−2, and average peak luminous efficiency of 0.35 cd/A. A green-emitting device had an average turn-on voltage of 4.6 V, average brightness at 10 V of 5500 cd m−2, and average peak luminous efficiency of 2.7 cd/A. A blue-emitting device had an average turn-on voltage of 5.7 V, average brightness at 10 V of 1380 cd m−2, and average peak luminous efficiency of 2.2 cd/A.
OLEDS were fabricated as described in Example 5 using the hydrolysate of Example 3. A red-emitting device had an average turn-on voltage of 7.3 V, average brightness at 10 V of 113 cd m−2, and average peak luminous efficiency of 0.12 cd/A. A green-emitting device had an average turn-on voltage of 6.2 V, average brightness at 10 V of 977 cd m−2, and average peak luminous efficiency of 2.0 cd/A. A blue-emitting device had an average turn-on voltage of >10 V, average brightness at 10 V of 3.6 cd m−2, and average peak luminous efficiency of 0.11 cd/A.
OLEDS were fabricated as described in Example 5 using the hydrolysate of Example 4. A red-emitting device had an average turn-on voltage of 6.7 V, average brightness at 10 V of 170 cd m−2, and average peak luminous efficiency of 0.31 cd/A. A green-emitting device had an average turn-on voltage of 5.6 V, average brightness at 10 V of 1100 cd m−2, and average peak luminous efficiency of 1.8 cd/A. A blue-emitting device had an average turn-on voltage of 6.2 V, average brightness at 10 V of 740 cd m−2, and average peak luminous efficiency of 1.9 cd/A.
Claims (10)
1. A silicone composition comprising:
(A) a hydrolysis product prepared by reacting (a) at least one thiophenyl-substituted silane having the formula Th—(CH2)m+2SiR1 nX3-n, and (b) a cross-linking agent selected from (i) at least one silane having the formula (R3 bSiX4-b), (ii) at least one organic compound having an average of at least two silyl groups per molecule, wherein the silyl groups have the formula —SiR3 cX3-c, and (iii) a mixture comprising (i) and (ii), with water in the presence of an organic solvent to form an organic phase containing the hydrolysis product and an aqueous phase, and separating the organic phase from the aqueous phase, wherein R1 is C1 to C10 hydrocarbyl free of aliphatic unsaturation, X is a hydrolysable group, Th is thiophenyl or substituted thiophenyl, R3 is C1 to C10 hydrocarbyl or —H, m is 0 to 10, n is 0, 1, or 2, b is 0 or 1, and c is 0, 1, or 2; and
(B) an organic solvent.
2. The silicone composition according to claim 1 , wherein the subscript m has a value of from 0 to 5.
3. The silicone composition according to claim 1 , wherein Th is selected from thiophen-2-yl, 2,2′-bithiophen-5-yl, and 2,2′:5′,2″-terthiophen-5-yl.
4. The silicone composition according to claim 1 , wherein X in the formula of the thiophenyl-substituted silane and the cross-linking agent is selected from —Cl and —Br.
5. An organic light-emitting diode comprising:
a substrate having a first opposing surface and a second opposing surface;
a first electrode layer overlying the first opposing surface;
a light-emitting element overlying the first electrode layer, the light-emitting element comprising
an emissive/electron-transport layer, and
a hole-transport/hole-injection layer, wherein the hole-transport/hole-injection layer comprises a cured polysiloxane prepared by applying a silicone composition to form a film and curing the film, wherein the silicone composition comprises (A) a hydrolysis product prepared by reacting (a) at least one thiophenyl-substituted silane having the formula Th—(CH2)m+2SiR1 nX3-n, and (b) a cross-linking agent selected from (i) at least one silane having the formula (R3 bSiX4-b), (ii) at least one organic compound having an average of at least two silyl groups per molecule, wherein the silyl groups have the formula —SiR3 cX3-c, and (iii) a mixture comprising (i) and (ii), with water in the presence of an organic solvent to form an organic phase containing the hydrolysis product and an aqueous phase, and separating the organic phase from the aqueous phase, wherein R1 is C1 to C10 hydrocarbyl free of aliphatic unsaturation, X is a hydrolysable group, Th is thiophenyl or substituted thiophenyl, R3 is C1 to C10 hydrocarbyl or —H, m is 0 to 10, n is 0, 1, or 2, b is 0 or 1, and c is 0, 1, or 2; and (B) an organic solvent; and
a second electrode layer overlying the light-emitting element.
6. The organic light emitting diode according to claim 5 , wherein the subscript m has a value of from 0 to 5.
7. The organic light emitting diode according to claim 5 , wherein Th is selected from thiophen-2-yl, 2,2′-bithiophen-5-yl, and 2,2′:5′,2″-terthiophen-5-yl.
8. The organic light emitting diode according to claim 5 , wherein X in the formula of the thiophenyl-substituted silane and the cross-linking agent is selected from —Cl and —Br.
9. The organic light-emitting diode according to claim 5 , wherein the emmisive/electron transport layer comprises a fluorescent dye.
10. The organic light-emitting diode according to claim 5 , further comprising at least one of a hole-transport layer and an electron injection layer.
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EP (1) | EP2262861B1 (en) |
JP (1) | JP5513479B2 (en) |
KR (1) | KR101451607B1 (en) |
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US10032983B2 (en) | 2013-05-27 | 2018-07-24 | Merck Patent Gmbh | Electron transfer composition for use in an electron injection layer for organic electronic devices |
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EP2850122B1 (en) * | 2012-05-14 | 2018-08-01 | Momentive Performance Materials Inc. | High refractive index material |
EP3070755B1 (en) * | 2015-03-19 | 2022-10-12 | Soongsil University Research Consortium Techno-Park | Method for manufacturing an organic semiconductor composition |
US10991894B2 (en) | 2015-03-19 | 2021-04-27 | Foundation Of Soongsil University-Industry Cooperation | Compound of organic semiconductor and organic semiconductor device using the same |
EP4186947B1 (en) * | 2021-11-26 | 2024-06-19 | Henkel AG & Co. KGaA | Polyorganosiloxane having heteroatom-containing silyl group |
EP4230690A1 (en) * | 2022-02-18 | 2023-08-23 | Henkel AG & Co. KGaA | Curable polymer compositions comprising heteroatom-containing silane compounds |
WO2024135316A1 (en) * | 2022-12-23 | 2024-06-27 | Jsr株式会社 | Composition, and method for producing semiconductor substrate |
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Also Published As
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JP2011515562A (en) | 2011-05-19 |
CN102015900A (en) | 2011-04-13 |
CN102015900B (en) | 2012-11-07 |
JP5513479B2 (en) | 2014-06-04 |
WO2009120434A1 (en) | 2009-10-01 |
KR20100139078A (en) | 2010-12-31 |
EP2262861B1 (en) | 2012-09-19 |
EP2262861A1 (en) | 2010-12-22 |
KR101451607B1 (en) | 2014-10-16 |
US20110017986A1 (en) | 2011-01-27 |
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